CN101684075A

CN101684075A - Metal complex ligand, metal complex, preparation method and application thereof, high molecular polymer, preparation method and application thereof

Info

Publication number: CN101684075A
Application number: CN200910175790A
Authority: CN
Inventors: 詹正云
Original assignee: Individual
Current assignee: Shanghai Zannan Technology Co ltd; Zhejiang Zansheng New Materials Co ltd
Priority date: 2008-09-27
Filing date: 2009-09-27
Publication date: 2010-03-31
Anticipated expiration: 2029-09-27
Also published as: CN104262590B; CN104211735A; CN101684075B; CN104262403B; CN104262590A; CN104211735B; CN104262403A

Abstract

The invention discloses a metal complex ligand, a metal complex, a preparation method and application thereof. Structural formulas of the metal (M) complex ligand Ia-Ic and the metal complex IIa-IIc thereof are shown. The metal complex has the advantages of higher catalytic activity, diversity of structures and physical properties and the like, and provides diverse optimal selection to catalytic application of various raw materials. The invention also discloses various novel functional polymer materials generated by ring-opening metathesis polymerization (ROMP) of different types of small molecular cycloolefines and application thereof, and structures of the materials are shown above.

Description

A kind of metal complex part, metal complex and its production and application, high molecular polymer and its production and application

Technical field

The present invention relates to a kind of part, complex compound and its production and application, a kind of polymkeric substance and its production and application is specifically related to a kind of metal complex part, metal complex and its production and application, a kind of high molecular polymer and its production and application.

Background technology

The research and development of olefin metathesis metathesis ruthenium catalyst and utilize the method for new and effective ruthenium complex catalyst by olefin catalytic metathesis ring-opening polymerization (ROMP:Ring Opening MetathesisPolymerization) to prepare multifunctional macromolecule novel material such as all kinds of high strength and high hardness to have caused widely and pay attention to.The seminars such as originator Grubbs of ruthenium complex catalyst have reported dissimilar ruthenium complex catalysts and have prepared all kinds of multi-functional polymer novel materials by associated olefinic catalysis metathesis ring-opening polymerization and reaction and injection molding process (RIM:Reaction Injection Molding) technology in this field, and the key that wherein prepares all kinds of multifunctional macromolecule novel materials is effective ROMP catalyzer.

Olefin catalytic polymerization product (ROMP-RIM) has higher resistance to impact shock and modulus in flexure, be difficult for temperature influence, fabulous erosion resistance is arranged, very good mechanical properties such as low density all have broad application prospects in fields such as traffic, electric installation, sports and amusement facility, civil construction material, casting, communications.Present main ROMP new material industry manufacturer is the ZEON company that Nobel laureate professor Grubbs provides Hercules company, Goodrich company and the Japan of the U.S. Materia Inc. of ROMP patented technology and the U.S..

Some present olefin catalytic polymerization products have obtained industrial applications, but the method for its shortcoming by the ruthenium catalyst ring-opening polymerization prepares the intensity of all kinds of multi-functional polymer novel materials and modulus etc. to be in above the average, remain further to research and develop more effective alkene ring-opening polymerization catalyst and polymerization reaction monomer and complete processing, reach the purpose that improves mechanical property.

Summary of the invention

The present invention is in order to solve the shortcoming of existing olefin metathesis reaction catalyzer and associated olefinic catalysis metathesis ring-opening polymerization, and the performance that improves the olefin metathesis reaction catalyzer by research and development improves mechanical propertys such as the intensity of olefinic polymerization product and modulus.The feature of novel metal complexes part of the present invention is that the part that is constituted with Sauerstoffatom and/or nitrogen-atoms can form the metal complex catalyst of stablizing and have greater activity with metal especially ruthenium ion, that the present invention has introduced in metal complex catalyst is dissimilar, the part of different physical characteristics, different catalytically active, thereby, provide the selection of more catalysis techniques for the optimization of olefin metathesis reaction and products thereof for the synthetic preparation of chemical industry, medicine and polymer novel material provides the metal complex catalyst of more effective various, different activities.

Therefore, one of purpose of the present invention provides the olefin metathesis metal complex part that a kind of structural formula is formula Ia, Ib, Ic:

Wherein, Z is CH ₂Or

M=0 or 1, n=0 or 1;

During n=1, X ¹And Y ¹Be nitrogen, oxygen, sulphur, CH independently ₂, replacement or unsubstituted C ₁-C ₂₀Alkyl, replacement or unsubstituted C ₆-C ₂₀Aryl, replacement or unsubstituted C ₆-C ₂₀Aryloxy, replacement or unsubstituted C ₂-C ₂₀Heterocyclic aryl, carbonyl, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₂₀Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀Aryl, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₁-C ₂₀Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; X ¹The parent that each group of expression connects is Y ¹, the part that wherein connects Y can be each group itself, also can be the various substituting groups of group, Y ¹The parent that each group of expression connects is X ¹, wherein connect R ₂Part can be group itself, also can be the various substituting groups of group;

During m=0, Y is nitrogen, oxygen, replacement or unsubstituted C ₁-C ₂₀Alkoxyl group, replacement or unsubstituted C ₆-C ₂₀Aryloxy, replacement or unsubstituted C ₂-C ₂₀Heterocyclic aryl, carbonyl, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₂₀Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀Aryl, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₁-C ₂₀Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; Among the formula Ia, the parent that the group that Y represents connects is X, and the part that wherein connects the other end can be each group itself, also can be the various substituting groups of group; Among the formula Ib, the parent that the group that Y represents connects is an aromatic ring, and the parent that the group that Y represents among the Ic connects is for connecting R ₃Carbon;

During m=1, X is nitrogen, oxygen, sulphur, CH, CH ₂, carbonyl; Y is nitrogen, oxygen, CH, methylene radical, replacement or unsubstituted C ₁-C ₂₀Alkoxyl group, replacement or unsubstituted C ₆-C ₂₀Aryl, replacement or unsubstituted C ₆-C ₂₀Aryloxy, replacement or unsubstituted C ₂-C ₂₀Heterocyclic aryl, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₂₀Alkyl imido grpup, unsubstituted C ₁-C ₂₀Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀Aryl, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₁-C ₂₀Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; The parent that the group that X represents connects is Y, and the part that wherein connects the other end can be each group itself, also can be the various substituting groups of group; The parent that the group that Y represents connects is X, and the part that wherein connects the other end can be each group itself, also can be the various substituting groups of group; Can be singly-bound or two key between " X=Y ";

R ¹Be hydrogen, replacement or unsubstituted C ₁-C ₂₀Alkyl, replacement or unsubstituted C ₁-C ₂₀Alkoxyl group, replacement or unsubstituted C ₁-C ₂₀Alkylthio, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkoxyl group, connection replace or unsubstituted C ₆-C ₂₀The carbonyl of aryloxy, connection replace or unsubstituted C ₆-C ₂₀The carbonyl of heterocyclyloxy base, replacement or unsubstituted C ₆-C ₂₀Aryl, replacement or unsubstituted C ₆-C ₂₀Aryloxy or replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical;

R ²Be hydrogen, replacement or unsubstituted C ₁-C ₂₀Alkyl, replacement or unsubstituted C ₁-C ₂₀Alkoxyl group, replacement or unsubstituted C ₁-C ₂₀Alkylthio, replacement or unsubstituted C ₁-C ₂₀Alkyl siloxy, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₆-C ₂₀Aryl, C ₆-C ₂₀Aryloxy, aldehyde radical, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkyl, connection replace or unsubstituted C ₆-C ₂₀The carbonyl of aryl, connection replace or unsubstituted C ₂-C ₂₀The carbonyl of heterocyclic radical or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, formyl radical, replacement or unsubstituted C independently ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring;

R ³Be hydrogen, replacement or unsubstituted C ₁-C ₂₀Alkyl, replacement or unsubstituted C ₁-C ₂₀Alkoxyl group, replacement or unsubstituted C ₁-C ₂₀Alkylthio, C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₆-C ₂₀Aryl, replacement or unsubstituted C ₆-C ₂₀Aryloxy, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkoxyl group, connection replace or unsubstituted C ₆-C ₂₀The carbonyl of aryloxy, connection replace or unsubstituted C ₆-C ₂₀The carbonyl of heterocyclyloxy base or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, formyl radical, replacement or unsubstituted C independently ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring;

E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C ₁-C ₂₀Alkyl, C ₁-C ₂₀Alkoxyl group, C ₁-C ₂₀Alkylthio, C ₁-C ₂₀Silica-based, the C of alkane ₁-C ₂₀Alkyl siloxy, C ₂-C ₂₀Heterocyclic radical, C ₆-C ₂₀Aryl, C ₆-C ₂₀Aryloxy, connection C ₁-C ₂₀The carbonyl of alkyl, connection C ₆-C ₂₀The carbonyl of aryl, connection C ₂-C ₂₀The carbonyl of heterocyclic radical, connection C ₁-C ₂₀The carbonyl of alkoxyl group, connection C ₆-C ₂₀The carbonyl of aryloxy, connection C ₆-C ₂₀The carbonyl of heterocyclyloxy base, aminoacyl, connection C ₁-C ₂₀The carbonyl of alkylamino, connection C ₆-C ₂₀The carbonyl of arylamino, connection C ₂-C ₂₀The carbonyl of heterocyclic radical amino, urea groups, replacement or unsubstituted C ₁-C ₂₀Alkyl urea groups, replacement or unsubstituted C ₆-C ₂₀Aryl-ureido, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical urea groups, connection C ₁-C ₂₀The alkylsulfonyl of alkylamino, connection C ₆-C ₂₀The alkylsulfonyl of arylamino, connection C ₂-C ₂₀The alkylsulfonyl of heterocyclic radical amino or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀Aryl, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₁-C ₂₀Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl sulphonyl, replacement or unsubstituted C ₆-C ₂₀Aryl sulfonyl or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring;

E ¹Be hydrogen, halogen, nitro, itrile group, C ₁-C ₂₀Alkyl, C ₁-C ₂₀Alkoxyl group, C ₁-C ₂₀Alkylthio, C ₁-C ₂₀Silica-based, the C of alkane ₁-C ₂₀Alkyl siloxy, C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted amino, aminoacyl, connection C ₁-C ₂₀The carbonyl of alkylamino, C ₆-C ₂₀Aryl, C ₆-C ₂₀Aryloxy, sulfoxide group, sulfuryl, aldehyde radical, connection C ₁-C ₂₀The carbonyl of alkyl, connection replace or unsubstituted C ₆-C ₂₀The carbonyl of aryl, connection replace or unsubstituted C ₂-C ₂₀The carbonyl of heterocyclic radical, connection C ₁-C ₂₀The carbonyl of alkoxyl group, connection C ₆-C ₂₀The carbonyl of arylamino, connection C ₂-C ₂₀The carbonyl of heterocyclic radical amino, urea groups, replacement or unsubstituted C ₁-C ₂₀Alkyl urea groups, replacement or unsubstituted C ₁-C ₂₀Alkyl urea groups, replacement or unsubstituted C ₆-C ₂₀Aryl-ureido or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical urea groups;

E ²Be hydrogen, halogen, C ₁-C ₂₀Alkyl, C ₁-C ₂₀Alkoxyl group, C ₁-C ₂₀Alkylthio, C ₁-C ₂₀Silica-based, the C of alkane ₁-C ₂₀Alkyl siloxy, aminoacyl, connection C ₁-C ₂₀The carbonyl of alkylamino, connection C ₆-C ₂₀The carbonyl of arylamino, connection C ₂-C ₂₀The carbonyl of heterocyclic radical amino, C ₆-C ₂₀Aryl, C ₆-C ₂₀Aryloxy, C ₂-C ₂₀Heterocyclic aryl, aldehyde radical, connection C ₁-C ₂₀The carbonyl of alkyl, connection C ₆-C ₂₀The carbonyl of aryl, connection C ₂-C ₂₀The carbonyl of heterocyclic radical, connection C ₁-C ₂₀The carbonyl of alkoxyl group, connection C ₆-C ₂₀The carbonyl of aryloxy, connection C ₂-C ₂₀The carbonyl of heterocyclic radical amino or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀Aryl, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₁-C ₂₀Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl sulphonyl, replacement or unsubstituted C ₆-C ₂₀Aryl sulfonyl or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring;

E ³Be hydrogen, halogen, C ₁-C ₂₀Alkyl, C ₁-C ₂₀Alkoxyl group, C ₁-C ₂₀Alkylthio, C ₁-C ₂₀Alkyl siloxy, C ₆-C ₂₀Aryloxy, C ₆-C ₂₀Aryl, C ₂-C ₂₀Heterocyclic aryl, connection C ₁-C ₂₀The carbonyl of alkoxyl group, connection replace or unsubstituted C ₆-C ₂₀The carbonyl of aryloxy, connection replace or unsubstituted C ₆-C ₂₀The carbonyl of heterocyclyloxy base or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀Aryl, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₁-C ₂₀Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl sulphonyl, replacement or unsubstituted C ₆-C ₂₀Aryl sulfonyl or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring;

E ⁴, E ⁵, E ⁶And E ⁷Be hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, replacement or unsubstituted C independently ₁-C ₂₀Alkyl, replacement or unsubstituted C ₁-C ₂₀Alkoxyl group, C ₁-C ₂₀Alkylthio, C ₁-C ₂₀Silica-based, the C of alkane ₁-C ₂₀Alkane siloxy, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted amino, aminoacyl, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkylamino, connection replace or unsubstituted C ₆-C ₂₀The carbonyl of arylamino, connection replace or unsubstituted C ₂-C ₂₀The carbonyl of heterocyclic radical amino, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkyl, connection replace or unsubstituted C ₆-C ₂₀The carbonyl of aryl, connection replace or unsubstituted C ₂-C ₂₀The carbonyl of heterocyclic radical, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkoxyl group, connection replace or unsubstituted C ₆-C ₂₀The carbonyl of aryloxy, connection replace or unsubstituted C ₆-C ₂₀The carbonyl of heterocyclyloxy base, urea groups, replacement or unsubstituted C ₁-C ₂₀Alkyl urea groups, replacement or unsubstituted C ₁-C ₂₀Alkyl urea groups, replacement or unsubstituted C ₆-C ₂₀Aryl-ureido or replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical urea groups, replacement or unsubstituted C ₆-C ₂₀Aryl, replacement or unsubstituted C ₆-C ₂₀Aryloxy or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀Aryl, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₁-C ₂₀Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl sulphonyl, replacement or unsubstituted C ₆-C ₂₀Aryl sulfonyl or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring.

Among the present invention, preferable, in formula Ia, Ib, Ic,

Z is CH ₂Or TsNHN=;

M=0 or 1, n=0 or 1;

During n=1, X ¹And Y ¹Be nitrogen, oxygen, sulphur, CH independently ₂, replacement or unsubstituted C ₁-C ₁₅Alkyl, replacement or unsubstituted C ₆-C ₁₅Aryl, replacement or unsubstituted C ₆-C ₁₅Aryloxy, replacement or unsubstituted C ₂-C ₁₅Heterocyclic aryl, carbonyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₁₅Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₁₅Aryl, replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical, replacement or unsubstituted C ₁-C ₁₅Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₁₅Alkyl formyl radical, replacement or unsubstituted C ₆-C ₁₅Aryl formyl radical or replacement or unsubstituted C ₂-C ₁₅The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; X ¹The parent that each group of expression connects is Y ¹, the part that wherein connects the other end can be each group itself, also can be the various substituting groups of group; Y ¹The parent that each group of expression connects is X ¹, the part that wherein connects the other end can be each group itself, also can be the various substituting groups of group;

During m=0, Y is nitrogen, oxygen, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₆-C ₁₅Aryloxy, replacement or unsubstituted C ₂-C ₁₅Heterocyclic aryl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₁₅Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₁₅Aryl, replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical, replacement or unsubstituted C ₁-C ₁₅Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₁₅Alkyl formyl radical, replacement or unsubstituted C ₆-C ₁₅Aryl formyl radical or replacement or unsubstituted C ₂-C ₁₅The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; Among the formula Ia, the parent that the group that Y represents connects is X, and the part that wherein connects the other end can be each group itself, also can be the various substituting groups of group; Among the formula Ib, the parent that the group that Y represents connects is an aromatic ring, and the parent that the group that Y represents among the Ic connects is for connecting R ₃Carbon;

During m=1, X is nitrogen, oxygen, sulphur, CH, CH ₂, carbonyl; Y is nitrogen, oxygen, CH, methylene radical, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₆-C ₁₅Aryl, replacement or unsubstituted C ₆-C ₁₅Aryloxy, replacement or unsubstituted C ₂-C ₁₅Heterocyclic aryl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, replacement or unsubstituted C ₁-C ₁₅Imido grpup; Suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₁₅Aryl, replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical, replacement or unsubstituted C ₁-C ₁₅Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₁₅Alkyl formyl radical, replacement or unsubstituted C ₆-C ₁₅Aryl formyl radical or replacement or unsubstituted C ₂-C ₁₅The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; The parent that the group that X represents connects is Y, and the part that wherein connects the other end can be each group itself, also can be the various substituting groups of group; The parent that the group that Y represents connects is X, and the part that wherein connects the other end can be each group itself, also can be the various substituting groups of group; Can be singly-bound or two key between " X=Y ";

R ¹Be hydrogen, replacement or unsubstituted C ₁-C ₁₅Alkyl, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₁-C ₁₅Alkylthio, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, replacement or unsubstituted C ₆-C ₁₅Aryl, replacement or unsubstituted C ₆-C ₁₅Aryloxy or replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical;

R ²Be hydrogen, replacement or unsubstituted C ₁-C ₁₅Alkyl, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₁-C ₁₅Alkylthio, replacement or unsubstituted C ₁-C ₁₅Alkane siloxy, replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical, C ₆-C ₁₅Aryl, C ₆-C ₁₅Aryloxy, aldehyde radical, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, formyl radical, replacement or unsubstituted C independently ₁-C ₁₅Alkyl formyl radical, replacement or unsubstituted C ₆-C ₁₅Aryl formyl radical or replacement or unsubstituted C ₂-C ₁₅The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring;

R ³Be hydrogen, replacement or unsubstituted C ₁-C ₁₅Alkyl, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₁-C ₁₅Alkylthio, replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical, replacement or unsubstituted C ₆-C ₁₅Aryl, replacement or unsubstituted C ₆-C ₁₅Aryloxy, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, formyl radical, replacement or unsubstituted C independently ₁-C ₁₅Alkyl formyl radical, replacement or unsubstituted C ₆-C ₁₅Aryl formyl radical or replacement or unsubstituted C ₂-C ₁₅The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring;

E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C ₁-C ₁₅Alkyl, C ₁-C ₁₅Alkoxyl group, C ₁-C ₁₅Alkylthio, C ₁-C ₁₅Silica-based, the C of alkane ₁-C ₁₅Alkane siloxy, C ₂-C ₁₅Heterocyclic radical, C ₆-C ₁₅Aryl, C ₆-C ₁₅Aryloxy, connection C ₁-C ₁₅The carbonyl of alkyl, connection C ₆-C ₁₅The carbonyl of aryl, connection C ₂-C ₁₅The carbonyl of heterocyclic radical, connection C ₁-C ₁₅The carbonyl of alkoxyl group, aminoacyl, connection C ₁-C ₁₅The carbonyl of alkylamino, connection C ₆-C ₁₅The carbonyl of arylamino, connection C ₂-C ₁₅The carbonyl of heterocyclic radical amino, urea groups, replacement or unsubstituted C ₁-C ₁₅Alkyl urea groups or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, aryl, C independently ₂-C ₂₀Heterocyclic radical, C ₁-C ₂₀Alkyl, formyl radical, C ₁-C ₁₅Alkyl formyl radical, C ₆-C ₁₅Aryl formyl radical, C ₂-C ₁₅Heterocyclic radical formyl radical, C ₁-C ₁₅Alkyl sulphonyl, C ₆-C ₂₀Aryl sulfonyl or C ₂-C ₂₀The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring;

E ¹Be hydrogen, halogen, nitro, sulfuryl, C ₁-C ₁₅Alkyl, C ₁-C ₁₅Alkoxyl group, C ₁-C ₁₅Alkylthio, C ₁-C ₁₅Silica-based, the C of alkane ₁-C ₁₅Alkane siloxy, C ₂-C ₁₅Heterocyclic radical, C ₆-C ₁₅Aryl, C ₆-C ₁₅Aryloxy, aldehyde radical, connection C ₁-C ₁₅The carbonyl of alkyl, connection C ₁-C ₁₅The carbonyl of alkoxyl group, aminoacyl, connection C ₁-C ₁₅The carbonyl of alkylamino, urea groups, replacement or unsubstituted C ₁-C ₁₅Alkyl urea groups, replacement or unsubstituted C ₁-C ₁₅Alkyl, connection C ₁-C ₁₅Amino alkylsulfonyl or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, aryl, C independently ₂-C ₂₀Heterocyclic radical, C ₁-C ₂₀Alkyl, formyl radical, C ₁-C ₁₅Alkyl formyl radical, C ₆-C ₁₅Aryl formyl radical, C ₂-C ₁₅Heterocyclic radical formyl radical, C ₁-C ₁₅Alkyl sulphonyl, C ₆-C ₂₀Aryl sulfonyl or C ₂-C ₂₀The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring;

E ²Be hydrogen, halogen, C ₁-C ₁₅Alkyl, C ₁-C ₁₅Alkoxyl group, C ₁-C ₁₅Alkylthio, C ₁-C ₁₅Silica-based, the C of alkane ₁-C ₁₅Alkane siloxy, C ₆-C ₁₅Aryl, C ₆-C ₁₅Aryloxy, C ₂-C ₁₅Heterocyclic aryl, aldehyde radical, connection C ₁-C ₁₅The carbonyl of alkyl, connection C ₁-C ₁₅The carbonyl of alkoxyl group, aminoacyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkylamino or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, C independently ₆-C ₁₅Aryl, C ₂-C ₁₅Heterocyclic radical, C ₁-C ₁₅Alkyl, formyl radical, C ₁-C ₁₅Alkyl formyl radical, C ₆-C ₁₅Aryl formyl radical, C ₂-C ₁₅The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring;

E ³Be hydrogen, halogen, C ₁-C ₁₅Alkyl, C ₁-C ₁₅Alkoxyl group, C ₁-C ₁₅Alkylthio, C ₁-C ₁₅Alkane siloxy, C ₆-C ₁₅Aryl, C ₆-C ₁₅Aryloxy, C ₂-C ₁₅Heterocyclic aryl, connection C ₁-C ₁₅The carbonyl of alkoxyl group, aminoacyl, connection C ₁-C ₁₅The carbonyl of alkylamino or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, C independently ₆-C ₁₅Aryl, C ₂-C ₁₅Heterocyclic radical, replacement or unsubstituted C ₁-C ₁₅Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₁₅Alkyl formyl radical, replacement or unsubstituted C ₆-C ₁₅The aryl formyl radical; Perhaps Rc, Rd and N atom connect into ring;

E ⁴, E ⁵, E ⁶And E ⁷Be hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, replacement or unsubstituted C independently ₁-C ₁₅Alkyl, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, C ₁-C ₁₅Alkylthio, C ₁-C ₁₅Silica-based, the C of alkane ₁-C ₁₅Alkane siloxy, replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical, aminoacyl, connection C ₁-C ₁₅The carbonyl of alkylamino, connection C ₆-C ₁₅The carbonyl of arylamino, connection C ₂-C ₁₅The carbonyl of heterocyclic radical amino, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, urea groups, replacement or unsubstituted C ₁-C ₁₅Alkyl urea groups, replacement or unsubstituted C ₁-C ₁₅Alkylsulfonamido, connection C ₁-C ₁₅The sulphonyl of alkylamino, replacement or unsubstituted C ₆-C ₁₅Aryl, replacement or unsubstituted C ₆-C ₁₅Aryloxy or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀Aryl, replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical, replacement or unsubstituted C ₁-C ₁₅Alkyl, formyl radical, C ₁-C ₁₅Alkyl formyl radical, C ₆-C ₁₅Aryl formyl radical, C ₂-C ₁₅Heterocyclic radical formyl radical, replacement or unsubstituted C ₁-C ₁₅Alkyl sulphonyl, replacement or unsubstituted C ₆-C ₁₅Aryl sulfonyl or replacement or unsubstituted C ₂-C ₁₅The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring.

Among the present invention, better, in formula Ia, Ib, Ic,

Z is CH ₂Or

M=0 or 1, n=0 or 1;

During n=1, X ¹Be oxygen, CH ₂, replacement or unsubstituted C ₆-C ₁₂Aryl; Y ¹For oxygen, nitrogen, carbonyl, connection replace or unsubstituted C ₁-C ₈The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₈The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₈Imino-; Wherein, X ¹The parent that each group of expression connects is Y ¹, Y ¹The parent that each group of expression connects is X ¹

During m=0, Y is nitrogen, oxygen, carbonyl, connection replacement or unsubstituted C ₁-C ₈The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₈The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₈Imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₁-C ₈Aryl, replacement or unsubstituted C ₂-C ₁₂Heterocyclic radical or replacement or unsubstituted C ₁-C ₈Alkyl; Perhaps Rc, Rd and N atom connect into ring; Among the formula Ia, the parent that the group that Y represents connects is X, and among the formula Ib, the parent that the group that Y represents connects is an aromatic ring, and the parent that the group that Y represents among the Ic connects is for connecting R ₃Carbon;

During m=1, X is nitrogen, oxygen, methyne, methylene radical, carbonyl; Y is nitrogen, oxygen, replacement or unsubstituted C ₆-C ₁₂Aryl, connection replace or unsubstituted C ₁-C ₈The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₈The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₈Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₁₂Aryl, replacement or unsubstituted C ₂-C ₁₂Heterocyclic radical or replacement or unsubstituted C ₁-C ₈Alkyl; Perhaps Rc, Rd and N atom connect into ring; The parent that the group that X represents connects is Y, and the part that wherein connects the other end can be each group itself, also can be the various substituting groups of group; The parent that the group that Y represents connects is X, and the part that wherein connects the other end can be each group itself, also can be the various substituting groups of group; Can be singly-bound or two key between " X=Y ";

R ¹Be hydrogen or replacement or unsubstituted C ₆-C ₁₂Aryl;

R ²Be methyl, sec.-propyl, replacement or unsubstituted C ₁-C ₈Alkyl or replacement or unsubstituted C ₆-C ₁₂Aryl;

R ³Be hydrogen, replacement or unsubstituted C ₁-C ₈Alkyl, replacement or unsubstituted C ₁-C ₈Alkoxyl group, C ₆-C ₁₂Aryl, C ₆-C ₁₂Aryloxy, C ₂-C ₁₂Heterocyclic aryl, connection C ₁-C ₈The carbonyl of alkoxyl group or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, formyl radical, replacement or unsubstituted C independently ₁-C ₈Alkyl formyl radical, replacement or unsubstituted C ₆-C ₁₂Aryl formyl radical or replacement or unsubstituted C ₂-C ₁₂The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring;

E is hydrogen, halogen, nitro, C ₁-C ₈Alkyl, C ₁-C ₈Alkoxyl group, C ₆-C ₁₂Aryl, connection C ₁-C ₈The carbonyl of alkyl, connection C ₁-C ₈The carbonyl of alkoxyl group, connection C ₁-C ₈The carbonyl of alkylamino, connection C ₁-C ₈The carbonyl of alkylamino, connection C ₆-C ₁₂The carbonyl of arylamino, connection C ₂-C ₁₂The carbonyl of heterocyclic radical amino, connection replace or unsubstituted C ₁-C ₈The alkylsulfonyl of alkyl amine group;

Or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, aryl, C independently ₂-C ₁₂Heterocyclic radical, C ₁-C ₈Alkyl, formyl radical, C ₁-C ₈Alkyl formyl radical, C ₆-C ₁₂Aryl formyl radical, C ₂-C ₁₂Heterocyclic radical formyl radical, replacement or unsubstituted C ₁-C ₈Alkyl sulphonyl, replacement or unsubstituted C ₆-C ₁₂Aryl sulfonyl or replacement or unsubstituted C ₂-C ₁₂The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring;

E ¹Be hydrogen, halogen, nitro, C ₁-C ₈Alkyl, C ₁-C ₈Alkoxyl group, connection C ₁-C ₈The carbonyl of alkylamino, C ₆-C ₁₂Aryl, C ₆-C ₁₂Aryloxy, connection C ₁-C ₈The carbonyl of alkoxyl group or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, C independently ₆-C ₁₂Aryl, C ₂-C ₁₂Heterocyclic radical, C ₁-C ₈Alkyl, formyl radical, C ₁-C ₈Alkyl formyl radical, C ₆-C ₁₂Aryl formyl radical, C ₂-C ₁₂Heterocyclic radical formyl radical, replacement or unsubstituted C ₁-C ₈Alkyl sulphonyl, replacement or unsubstituted C ₆-C ₈Aryl sulfonyl or replacement or unsubstituted C ₂-C ₁₂The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring;

E ²Be hydrogen, halogen, C ₁-C ₈Alkyl, C ₁-C ₈Alkoxyl group, C ₆-C ₁₂Aryl, C ₆-C ₁₂Aryloxy, C ₂-C ₁₂Heterocyclic aryl, connection replace or unsubstituted C ₁-C ₈The carbonyl of alkoxyl group or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, C independently ₆-C ₁₂Aryl, C ₂-C ₁₂Heterocyclic radical, C ₁-C ₈Alkyl, formyl radical, C ₁-C ₈Alkyl formyl radical, C ₆-C ₁₂Aryl formyl radical, C ₂-C ₁₂The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring;

E ³Be hydrogen, halogen, C ₁-C ₈Alkyl, C ₁-C ₈Alkoxyl group, C ₆-C ₁₂Aryl, C ₆-C ₁₂Aryloxy, connection C ₁-C ₈The carbonyl of alkoxyl group or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, C independently ₆-C ₁₂Aryl, C ₂-C ₁₂Heterocyclic radical, replacement or unsubstituted C ₁-C ₈Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₈Alkyl formyl radical, replacement or unsubstituted C ₆-C ₁₂The aryl formyl radical; Perhaps Rc, Rd and N atom connect into ring;

E ⁴, E ⁵, E ⁶And E ⁷Be hydrogen, halogen, nitro, replacement or unsubstituted C independently ₁-C ₈Alkyl, replacement or unsubstituted C ₁-C ₈Alkoxyl group, replacement or unsubstituted C ₁-C ₈Alkylamino, formamido-, replacement or unsubstituted C ₁-C ₈Alkyl formamides base, connection C ₁-C ₈The carbonyl of alkylamino, connection C ₆-C ₁₂The carbonyl of arylamino, connection C ₂-C ₁₂The carbonyl of heterocyclic radical amino, connection C ₁-C ₈The carbonyl of alkoxyl group, sulfoamido, replacement or unsubstituted C ₆-C ₁₂Aryl, replacement or unsubstituted C ₆-C ₁₂Aryloxy or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀

Aryl, C ₂-C ₁₂Heterocyclic radical, C ₁-C ₈Alkyl, formyl radical, C ₁-C ₈Alkyl formyl radical, C ₆-C ₁₂Aryl formyl radical, C ₂-C ₁₂Heterocyclic radical formyl radical, replacement or unsubstituted C ₁-C ₈Alkyl sulphonyl, replacement or unsubstituted C ₆-C ₁₂Aryl sulfonyl, replacement or unsubstituted C ₂-C ₁₂The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring.

In best enforcement the of the present invention, among formula Ia, Ib and the Ic,

Z is CH ₂Or

N=0 or 1;

During n=1, X ¹Be CH ₂Or phenyl; Y ¹Be oxygen or carbonyl;

During m=0, Y is C ₁-C ₄Alkylamino or C ₁-C ₃Alkoxyl group;

During m=1, X is carbonyl, CH ₂, CH or phenmethyl; Y be nitrogen, NH,

C ₁-C ₄Alkoxyl group, C ₅Heterocyclic oxy group or C ₁-C ₃The alkane siloxy; Can be singly-bound or two key between X and the Y;

R ¹Phenyl for hydrogen, phenyl or nitro replacement;

R ²Be C ₁-C ₃Alkyl or C ₁-C ₃Alkoxyl group;

R ³Be hydrogen or C ₆Aryl;

E is halogen, nitro, C ₁-C ₄Alkyl, C ₁-C ₄Alkoxyl group, C ₁-C ₄Alkoxy carbonyl, C ₁-C ₈Alkyl amino sulfonyl, C ₆-C ₁₂N-aryl sulfonyl;

E ¹And E ²Be hydrogen, halogen, C independently ₁-C ₄Alkyl or C ₁-C ₄Alkoxyl group; E ³Be hydrogen;

E ⁴, E ⁵And E ⁷For being hydrogen, C independently ₁-C ₄Alkyl or C ₁-C ₄Alkoxyl group;

E ⁶Be hydrogen, halogen, C ₁-C ₄Alkyl or C ₁-C ₆Alkoxyl group;

Among the Ia, when n=0, R ²Be hydrogen, halogen, C ₁-C ₄Alkyl or C ₁-C ₄Alkoxyl group.

Two of purpose of the present invention provides the metal complex that a kind of structural formula is formula IIa, IIb, IIc:

Wherein, M is metal Ru (Ru), tungsten (W) or nickel (Ni);

L ¹And L ²Be halogen (Cl, Br independently ^-Or I), RCOO ^-Or ArO ^-Negatively charged ion;

L ³Be a kind of complex compound part of giving electronics;

L is a kind of complex compound part of giving electronics;

Wherein, Z is CH ₂Or

M=0 or 1, n=0 or 1; During n=0, p=0 or 1; During n=1, p=0;

E ²Be hydrogen, halogen, C ₁-C ₂₀Alkyl, C ₁-C ₂₀Alkoxyl group, C ₁-C ₂₀Alkylthio, C ₁-C ₂₀Silica-based, the C of alkane ₁-C ₂₀Alkyl siloxy, aminoacyl, connection C ₁-C ₂₀The carbonyl of alkylamino, connection C ₆-C ₂₀The carbonyl of arylamino, connection C ₂-C ₂₀The carbonyl of heterocyclic radical amino, C ₆-C ₂₀Aryl, C ₆-C ₂₀Aryloxy, C ₂-C ₂₀Heterocyclic aryl, aldehyde radical, connection C ₁-C ₂₀The carbonyl of alkyl, connection C ₆-C ₂₀The carbonyl of aryl, connection C ₂-C ₂₀The carbonyl of heterocyclic radical, connection C ₁-C ₂₀The carbonyl of alkoxyl group, connection C ₆-C ₂₀The carbonyl of arylamino, connection C ₂-C ₂₀The carbonyl of heterocyclic radical amino or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀Aryl, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₁-C ₂₀Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl sulphonyl, replacement or unsubstituted C ₆-C ₂₀Aryl sulfonyl or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring;

Among the present invention, that L is preferable among described IIa, IIb and the IIc is following structural IIIa, IIIb, IIIc or IIId:

Wherein, R ⁴And R ⁵Be C independently ₁-C ₂₀Alkyl, C ₆-C ₂₀Aryl, C ₁-C ₂₀Heterocyclic radical, aldehyde radical, connection C ₁-C ₂₀The carbonyl of alkyl, formamido-, C ₁-C ₂₀Alkyl formamides base, urea groups, replacement or unsubstituted C ₁-C ₂₀Alkyl urea groups, sulfoamido or C ₁-C ₂₀Alkylsulfonamido;

R ⁶And R ⁷Be hydrogen, C independently ₁-C ₂₀Alkyl, C ₁-C ₂₀Alkoxyl group, C ₁-C ₂₀Alkylthio, C ₁-C ₂₀Silica-based, the C of alkane ₁-C ₂₀Alkyl siloxy, C ₆-C ₂₀Aryl, C ₆-C ₂₀Aryloxy, C ₂-C ₂₀Heterocyclic radical, sulfoxide group, sulfuryl, aldehyde radical, connection C ₁-C ₂₀The carbonyl of alkyl, connection C ₁-C ₂₀The carbonyl of alkoxyl group, formamido-, C ₁-C ₂₀Alkyl formamides base, urea groups, replacement or unsubstituted C ₁-C ₂₀Alkyl urea groups, sulfoamido, C ₁-C ₂₀Alkylsulfonamido, halogen, nitro or itrile group;

R ⁸And R ⁹Independently for replacing or unsubstituted C ₁-C ₂₀Alkyl, C ₁-C ₂₀Alkoxyl group, C ₆-C ₂₀Aryl, C ₆-C ₂₀Aryloxy or C ₂-C ₂₀Heterocyclic radical;

Among the formula III a, preferable, R ⁴And R ⁵Be aryl; R ⁶And R ⁷Be hydrogen.

Better, the structural formula of L is formula III a or IIId; R ⁴And R ⁵Be mesityl; R ⁶And R ⁷Be hydrogen or IIId independently; R ⁸And R ⁹Be cyclohexyl.

In the another preferred embodiment of the present invention, among the formula II a-II c,

Metal (M) is a ruthenium;

L ¹And L ²Be chlorion;

L is IIIa or IIId; R wherein ⁴, R ⁵, R ⁶, R ⁷, R ⁸And R ⁹Identical with aforementioned definitions;

M=0 or 1, n=0 or 1; During n=0, p=0 or 1; During n=1, p=0;

During p=1, L ³Be the one or more substituted pyridyl in ortho position, a position and the contraposition, the nitrogen-atoms of pyridyl connects parent, and the substituting group of position and contraposition independently is halogen, nitro, itrile group, sulfoxide group, sulfuryl, C between pyridyl ₁-C ₁₅Alkyl, C ₁-C ₁₅Alkoxyl group, C ₁-C ₁₅Alkylthio, C ₁-C ₁₅Silica-based, the C of alkane ₁-C ₁₅Alkyl siloxy, C ₆-C ₁₅Aryloxy, C ₁-C ₁₅Alkyl amine group, replacement or unsubstituted C ₆-C ₁₅Aryl, replacement or unsubstituted C ₂-C ₁₅Heterocyclic aryl, carbonyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, formamido-, C ₁-C ₁₅Alkyl formamides base, urea groups, replacement or unsubstituted C ₁-C ₁₅Alkyl urea groups, sulfoamido or C ₁-C ₁₅Alkylsulfonamido;

During n=1, p=0, X ¹And Y ¹Be nitrogen, oxygen, sulphur, CH independently ₂, replacement or unsubstituted C ₁-C ₁₅Alkyl, replacement or unsubstituted C ₆-C ₁₅Aryl, replacement or unsubstituted C ₆-C ₁₅Aryloxy, replacement or unsubstituted C ₂-C ₁₅Heterocyclic aryl, carbonyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₁₅Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₁₅Aryl, replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical, replacement or unsubstituted C ₁-C ₁₅Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₁₅Alkyl formyl radical, replacement or unsubstituted C ₆-C ₁₅Aryl formyl radical or replacement or unsubstituted C ₂-C ₁₅The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; X ¹The parent that each group of expression connects is Y ¹, the part that wherein connects the other end can be each group itself, also can be the various substituting groups of group; Y ¹The parent that each group of expression connects is X ¹, the part that wherein connects the other end can be each group itself, also can be the various substituting groups of group;

Better, among the formula II a-II c,

M=0 or 1, n=0 or 1; During n=0, p=0 or 1; During n=1, p=0;

During p=1, L ³Be the one or more substituted pyridyl in ortho position, a position and the contraposition, the nitrogen-atoms of pyridyl connects parent, and the substituting group of position and contraposition independently is halogen, nitro, itrile group, sulfoxide group, sulfuryl, C between pyridyl ₁-C ₈Alkyl, C ₁-C ₈Alkoxyl group, C ₁-C ₈Alkylthio, C ₁-C ₈Silica-based, the C of alkane ₁-C ₈Alkyl siloxy, C ₆-C ₁₂Aryloxy, C ₁-C ₈Alkyl amine group, replacement or unsubstituted C ₆-C ₁₂Aryl, replacement or unsubstituted C ₂-C ₁₂Heterocyclic aryl, carbonyl, connection replace or unsubstituted C ₁-C ₈The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₈The carbonyl of alkoxyl group, formamido-, C ₁-C ₈Alkyl formamides base, urea groups, replacement or unsubstituted C ₁-C ₈Alkyl urea groups, sulfoamido or C ₁-C ₈Alkylsulfonamido;

During n=1, p=0, X ¹Be oxygen, CH ₂, replacement or unsubstituted C ₆-C ₁₂Aryl; Y ¹For oxygen, nitrogen, carbonyl, connection replace or unsubstituted C ₁-C ₈The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₈The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₈Imino-; Wherein, X ¹The parent that each group of expression connects is Y ¹, Y ¹The parent that each group of expression connects is X ¹

During m=0, Y is nitrogen, oxygen, carbonyl, connection replacement or unsubstituted C ₁-C ₈The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₈The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₈Imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₁₂Aryl, replacement or unsubstituted C ₂-C ₁₂Heterocyclic radical or replacement or unsubstituted C ₁-C ₈Alkyl; Perhaps Rc, Rd and N atom connect into ring; Among the formula Ia, the parent that the group that Y represents connects is X, and among the formula Ib, the parent that the group that Y represents connects is an aromatic ring, and the parent that the group that Y represents among the Ic connects is for connecting R ₃Carbon;

R ¹Be hydrogen or replacement or unsubstituted C ₆-C ₁₂Aryl;

E ⁴, E ⁵, E ⁶And E ⁷Be hydrogen, halogen, nitro, replacement or unsubstituted C independently ₁-C ₈Alkyl, replacement or unsubstituted C ₁-C ₈Alkoxyl group, replacement or unsubstituted C ₁-C ₈Alkylamino, formamido-, replacement or unsubstituted C ₁-C ₈Alkyl formamides base, connection C ₁-C ₈The carbonyl of alkylamino, connection C ₆-C ₁₂The carbonyl of arylamino, connection C ₂-C ₁₂The carbonyl of heterocyclic radical amino, connection C ₁-C ₈The carbonyl of alkoxyl group, sulfoamido, replacement or unsubstituted C ₆-C ₁₂Aryl, replacement or unsubstituted C ₆-C ₁₂Aryloxy or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₁₂Aryl, C ₂-C ₁₂Heterocyclic radical, C ₁-C ₈Alkyl, formyl radical, C ₁-C ₈Alkyl formyl radical, C ₆-C ₁₂Aryl formyl radical, C ₂-C ₁₂Heterocyclic radical formyl radical, replacement or unsubstituted C ₁-C ₈Alkyl sulphonyl, replacement or unsubstituted C ₆-C ₁₂Aryl sulfonyl, replacement or unsubstituted C ₂-C ₁₂The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring.

In of the present invention one best the enforcement, among the formula II a-II c,

M is a ruthenium; L is

Thricyclohexyl phosphorus; L ¹And L ²Be chlorine;

N=0 or 1;

During n=0, p=0 or 1; During n=1, p=0;

During p=1, L ³Be a position and/or the substituted pyridyl ligands of contraposition, the nitrogen-atoms of pyridyl connects parent, and the substituting group of position and contraposition is respectively halogen, C between pyridyl ₁-C ₃Alkoxyl group, C ₁-C ₆Alkyl amine group, replacement or unsubstituted C ₆-C ₁₂Aryl;

During n=1, p=0, X ¹Be CH ₂Or phenyl; Y ¹Be oxygen or carbonyl;

During m=0, Y is C ₁-C ₄Alkylamino or C ₁-C ₃Alkoxyl group;

During m=1, X is carbonyl, CH ₂, CH or phenmethyl; Y be nitrogen, NH,

R ¹Be hydrogen, C ₆The phenmethyl that aryl or nitro replace;

R ²Be C ₁-C ₃Alkyl or C ₁-C ₃Alkoxyl group;

R ³Be hydrogen or C ₆Aryl;

E ⁶Be hydrogen, halogen, C ₁-C ₄Alkyl or C ₁-C ₆Alkoxyl group;

Three of purpose of the present invention provides a kind of preparation method of metal complex, and it can be made by any of following three kinds of methods:

Method one comprises following three steps:

The structural formula of above-mentioned metal complex intermediate (Va, Vb, Vc) is as follows:

1) under protection of inert gas, replacement or unsubstituted tolysulfonyl hydrazone shown in SM-2 are generated the Cabbeen transition state in the anhydrous organic solvent of inorganic strong alkali; Wherein, R ^a, R ^b, R ^c, R ^dAnd R ^eAlone be hydrogen, C ₁-C ₈Alkyl or C ₁-C ₈Alkoxyl group;

2) under the protection of inert gas, Cabbeen transition state and ML that step 1) obtains ¹L ²(PPh) ₃Reaction generates the metal complex intermediate compound IV; Wherein, M, L ¹And L ²Definition each is described with claim 5-11, but L ¹And L ²All be not RCOO ^-

3) under the protection of inert gas, step 2) the metal complex intermediate that obtains and complex compound ligand i a, Ib or Ic reaction generates metal complex intermediate Va, Vb or Vc; Wherein, Va, Vb or Vc are that L is PPh among IIa, IIb or the IIc ₃The time compound, wherein M, L ¹, L ², Y, Y ¹, R ¹, R ², E, E ¹, E ²And E ³Ditto described;

Preferable, L ¹And L ²Be chlorine.

Wherein, in the step 1), described R ^a, R ^b, R ^c, R ^dAnd R ^eThe preferable hydrogen that is; Described inorganic strong alkali is preferable is in sodium methylate, sodium ethylate, sodium tert-butoxide and the sodium hydrogen one or more, and better is sodium ethylate; The consumption of described inorganic strong alkali is preferable be the SM-2 molar weight 1-3 doubly, better be 1.5-2 times; Described anhydrous organic solvent is preferable is in anhydrous methanol, ethanol, the trimethyl carbinol and the tetrahydrofuran (THF) one or more, and better is dehydrated alcohol; The consumption of described anhydrous organic solvent is preferable be the SM-2 molar weight 5-30 doubly, better is 15 times; What the temperature of described reaction was preferable is 45-75 ℃, and better is 55-65 ℃;

Step 2) in, what the temperature of described reaction was preferable is-50 ℃ to-85 ℃, and better is-65 ℃ to-75 ℃; Described ML ¹L ²L ₃Consumption preferable be the SM-2 molar weight 0.3-1.0 doubly, better be 0.6-0.7 times; Described ML ¹L ²(PPh) ₃That preferable is RuCl ₂P (Ph ₃) ₃

In the step 3), what the temperature of described reaction was preferable is-50 ℃ to-85 ℃, and better is-65 ℃ to-75 ℃; The consumption of described complex compound ligand i a, Ib or Ic is preferable be complex compound intermediate molar weight 1-3 doubly, better be 1.5-2 times;

Above-mentioned steps 1)-step 3) in, the time of reaction all with detection reaction fully till.

Work as ML ¹L ²L is RuCl ₂P (Ph ₃) ₃The time, the Va of generation, Vb and Vc are as follows:

Method two: with described in the method one Va, Vb or Vc under protection of inert gas respectively with except PPh ₃Outer other generate following metal complex IIa, IIb or IIc for the complex compound ligand L reaction of electronics, wherein, and p=0, M, L, L ¹, L ², Y, Y ¹, R ¹, R ², E, E ¹, E ²And E ³Definition ditto described, but L is not PPh ₃

Wherein, preferable, among metal complex IIa, the IIb or IIc of generation, L be thricyclohexyl phosphorus or

Mes=2,4, the 6-trimethylphenyl; What the temperature of described reaction was preferable is 20 ℃ to 75 ℃, and better when reacting with complex compound ligand i IIa is 60 ℃ to 75 ℃, and better when reacting with complex compound ligand i IId is 20 ℃ to 35 ℃; The consumption of described IIIa or IIId is preferable be complex compound intermediate Va, Vb or Vc molar weight 1-3 doubly, better be 1.5-2 times;

Method three: IIa, IIb or IIc are reacted generation following metal complex IIa, IIb or IIc with other the complex compound ligand L to electronics except thricyclohexyl phosphorus respectively under protection of inert gas; wherein; among IIa, the IIb or IIc as reactant: p=0, M, L ¹, L ², Y, Y ¹, R ¹, R ², E, E ¹, E ²And E ³Definition ditto described, L is a thricyclohexyl phosphorus; Among IIa, the IIb or IIc as resultant: p=0, M, L ¹, L ², Y, Y ¹, R ¹, R ², E, E ¹, E ²And E ³Definition ditto described, but L is not a thricyclohexyl phosphorus;

Method four: under the protection of inert gas, with method one resultant IIa, the IIb described in arbitrary method or IIc and complex compound ligand L of giving electronics to the method three ³Reaction generates IIa, IIb or IIc, wherein, and among the IIa of the resultant of present method, IIb or the IIc: p=1, M, L, L ¹, L ², L ³, Y, Y ¹, R ¹, R ², E, E ¹, E ²And E ³Ditto described; In the method four, what the temperature of described reaction was preferable is 20 ℃ to 35 ℃.

Method one is to method four, and is preferable, L ¹And L ²Be chlorine.

The normal condition that the method three here and each reaction conditions in the method four all react for this two class.

Among the present invention, when Z is CH ₂The time, metal complex ligand i a of the present invention can be obtained by following prepared in reaction:

Wherein, react the normal condition that each condition all can be this type of Suzuki reaction.In like manner, when Z be CH ₂The time, Ib and Ic also can be prepared by this class reaction.

Wherein Y, Y ¹, R ¹, R ², E, E ¹, E ², and E ³Definition with aforementioned.

Metal complex of the present invention can also be prior art by other two kinds of methods preparation, and their route is as follows:

The preparation method one:

Each reaction conditions in this route is the normal condition of these a few class reactions.

In this route, the Z among Ia, Ib or the Ic is tolysulfonyl-2-hydrazono-(TsNHN).Earlier the phenyl aldehyde and tolysulfonyl hydrazine reaction generation Ia, Ib or Ic that replaces from electron withdrawing groups such as amino-sulfonyl and sulphonamide under protection of inert gas, generates Cabbeen again in the ethanolic soln of sodium ethylate or sodium methylate, afterwards and RuCl ₂P (Ph ₃) ₃Reaction generates the ruthenium complex (Va-Vc) that contains triphenyl phosphorus; ruthenium complex (Va-Vc) generates part (L) with the thricyclohexyl phosphorus reaction again under protection of inert gas be the ruthenium complex (IIa-IIc) of IIId, is that the complex compound (IIa-IIc) of IIId is the better complex compound catalyst II of the catalytic activity a-II c of IIIa with five-ring part (IIIa) reaction generation part under protection of inert gas according to chemically reactive with complex compound (Va-Vc) or the part that makes.

The preparation method two:

Wherein: L=thricyclohexyl phosphorus or

IIa and IIb be path of preparing equally thus.Each reaction conditions in this route is the normal condition of these a few class reactions; Wherein, EWG is an electron-withdrawing group, L be thricyclohexyl phosphorus or

Mes is 2,4, the 6-trimethylphenyl.

Above-mentioned two kinds prepare in the route, and M is ruthenium (Ru), L ¹=L ²=Cl; Y, Y ¹, R ¹, R ², E, E ¹, E ², and E ³Definition the same.

Among the present invention, described heterocyclic radical is preferably heterocyclic aryl.

Four of purpose of the present invention provides the metal complex of above-mentioned formula II a-II c and make Application of Catalyst in the olefin metathesis replacement(metathesis)reaction.

What wherein, described olefin metathesis replacement(metathesis)reaction was preferable is olefin metathesis replacement(metathesis)reaction, intermolecular olefin metathesis replacement(metathesis)reaction (CM) or the intermolecular cycloolefin ring opening metathesis polymerization reaction (ROMP) of intramolecular cyclization.

The described cycloolefin that is used for olefinic polyreaction (ROMP) preferable for tensile cycloolefin structure or polycyclic olefin structure are arranged, described cycloolefin structure or polycyclic olefin structure are the structure of replacement or non-replacement, and they contain F, Cl, Br, N, O, Si, S, P, B, C in one or more rings ₆-C ₁₅Aromatic series and C ₄-C ₁₅In the aromatic heterocycle substituting group one or more.

In the preferred embodiments of the present invention, described cycloolefin structure contains 4 or 5 or 7-16 carbon atom, or a plurality of heteroatoms or heteroatom group; Described polycyclic olefin structure is the polycyclic olefin structure that contains 2 to 6 rings; Described polycyclic olefin is that one or more hydrogen in cyclopentadiene or its molecule are by C ₁-C ₁₅Saturated or undersaturated alkyl, replacement or unsubstituted C ₁-C ₁₅Amido, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₆-C ₁₅Aryloxy, replacement or unsubstituted C ₁-C ₁₅Heterocyclic oxy group, replacement or unsubstituted C ₁-C ₁₅Alkylthio, replacement or unsubstituted C ₆-C ₁₅Arylthio, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, methanoyl, formamido-, replacement or unsubstituted C ₁-C ₁₅Alkyl carbonyloxy, replacement or unsubstituted C ₁-C ₁₅Alkyl formamides base, replacement or unsubstituted C ₆-C ₁₅Aryl methanoyl or replacement or unsubstituted C ₆-C ₁₅The derivative that the aryl carboxamides base replaces.

In another preferred embodiments of the present invention, described polycyclic olefin is following polycyclic olefin structure VIa and VIb:

Wherein:

A is O, S, C ₁-C ₁₅Saturated or undersaturated alkyl, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₁-C ₁₅Aryloxy, replacement or unsubstituted C ₁-C ₁₅Heterocyclic oxy group, replacement or unsubstituted C ₁-C ₁₅Alkylthio, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, replacement or unsubstituted C ₁-C ₁₅Alkyl amine group, replacement or unsubstituted C ₁-C ₁₅Arylamine group, replacement or unsubstituted C ₁-C ₁₅Alkyl formamides base, replacement or unsubstituted C ₁-C ₁₅Aryl carboxamides base or replacement or unsubstituted C ₁-C ₁₅The heterocyclic radical formamido-;

R ¹⁰And R ¹¹Be hydrogen, halogen, replacement or unsubstituted C independently ₁-C ₁₅Alkyl, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₁-C ₁₅Alkylthio, replacement or unsubstituted C ₁-C ₁₅Alkane siloxy, C ₆-C ₁₅Aryloxy, C ₆-C ₁₅Aryl, C ₂-C ₁₅Heterocyclic radical, C ₂-C ₁₅Heterocyclic aryl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, formamido-, replacement or unsubstituted C ₁-C ₁₅Alkyl formamides base, C ₁-C ₁₅Alkylsulfonamido, urea groups, replacement or unsubstituted C ₁-C ₁₅Alkyl urea groups, ionic liquid monomer, liquid crystal monomer, active drug molecule; In formula VIa, R ¹⁰And R ¹¹Be not linked to be ring texture or be linked to be ring texture.

In another preferred embodiments of the present invention, described polycyclic olefin is following polycyclic olefin structure VIIa-VIIb:

Wherein:

A is O, S, C ₁-C ₁₅Saturated or undersaturated alkyl, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₁-C ₁₅Aryloxy, replacement or unsubstituted C ₁-C ₁₅Heterocyclic oxy group, replacement or unsubstituted C ₁-C ₁₅Alkylthio, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, formamido-, replacement or unsubstituted C ₁-C ₁₅Alkyl formamides base, replacement or unsubstituted C ₁-C ₁₅Aryl carboxamides base or replacement or unsubstituted C ₁-C ₁₅The heterocyclic radical formamido-;

R ¹²For replacing or unsubstituted C ₁-C ₁₅Alkyl, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₁-C ₁₅Alkylthio, replacement or unsubstituted C ₁-C ₁₅Alkane siloxy, C ₆-C ₁₅Aryloxy, C ₆-C ₁₅Aryl, C ₂-C ₁₅Heterocyclic radical, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, formamido-, replacement or unsubstituted C ₁-C ₁₅Formamido-, C ₁-C ₁₅Alkylsulfonamido, urea groups, replacement or unsubstituted C ₁-C ₁₅Alkyl urea groups, ionic liquid monomer, liquid crystal monomer or active drug molecule;

R ¹³And R ¹⁴Independently for replacing or unsubstituted C ₁-C ₁₅Alkyl, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₁-C ₁₅Alkylthio, replacement or unsubstituted C ₁-C ₁₅Alkane siloxy, C ₆-C ₁₅Aryloxy, C ₆-C ₁₅Aryl, C ₂-C ₁₅Heterocyclic radical, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, formamido-, replacement or unsubstituted C ₁-C ₁₅Formamido-, C ₁-C ₁₅Alkylsulfonamido, urea groups, replacement or unsubstituted C ₁-C ₁₅Alkyl urea groups, ionic liquid monomer, liquid crystal monomer or active drug molecule.

Among the present invention, the preferable polyreaction for the preparation macromolecule polymer material of described intermolecular cycloolefin ring opening metathesis polymerization reaction, the organic solvent of reaction is preferable is in methylene dichloride, ethylene dichloride, chloroform, toluene, dimethylbenzene, chlorobenzene and the ionic liquid one or more.When the raw material cycloolefin of reaction or polycyclic olefin when being liquid, can not add organic solvent.

In the another preferred embodiments of the present invention, the described high molecular polymer that is made by the reaction of intermolecular cycloolefin ring opening metathesis polymerization is for suc as formula shown in VIc, VId, VIe, VIIc, VIId, the Poly-DCPD;

Wherein, R ¹⁰, R ¹¹, R ¹², R ¹³And R ¹⁴Be hydrogen, halogen, nitro, itrile group, aldehyde radical, replacement or unsubstituted C independently ₁-C ₂₀Alkyl, C ₁-C ₂₀Alkoxyl group, replacement or unsubstituted C ₁-C ₂₀Aryloxy, C ₁-C ₂₀Heterocyclyloxy base, C ₁-C ₂₀Alkylthio, C ₁-C ₂₀Silica-based, the C of alkane ₁-C ₂₀Alkyl siloxy, C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₆-C ₂₀Aryl, C ₆-C ₂₀Aryloxy, connection C ₁-C ₂₀The carbonyl of alkyl, connection C ₆-C ₂₀The carbonyl of aryl, connection C ₂-C ₂₀The carbonyl of heterocyclic radical, connection C ₆-C ₂₀The carbonyl of aryloxy, connection C ₆-C ₂₀The carbonyl of heterocyclyloxy base, connection replace or unsubstituted C ₁-C ₂₀Oxygen base carbonyl, aminoacyl, connection saturated or unsaturated alkyl replace or unsubstituted C ₁-C ₂₀Saturated or unsaturated alkyl is amino carbonyl, connection C ₆-C ₂₀The carbonyl of arylamino, connection C ₂-C ₂₀The carbonyl of heterocyclic radical amino, urea groups, replacement or unsubstituted C ₁-C ₂₀Alkyl urea groups, replacement or unsubstituted C ₆-C ₂₀Aryl-ureido, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical urea groups, connection C ₁-C ₂₀The alkylsulfonyl of alkylamino, connection C ₆-C ₂₀The alkylsulfonyl of arylamino or connection C ₂-C ₂₀The alkylsulfonyl of heterocyclic radical amino; n ₁Be 10 ²-10 ⁴m ₁Be 10 ²-10 ⁴

Preferable, above-mentioned high molecular polymer is in formula VIc, VId, VIe, VIIc, VIId, Poly-DCPD:

R ¹⁰, R ¹¹, R ¹², R ¹³And R ¹⁴Be hydrogen, halogen, nitro, itrile group, aldehyde radical, replacement or unsubstituted C independently ₁-C ₁₅Alkyl, C ₁-C ₁₅Alkoxyl group, C ₁-C ₁₅Heterocyclic oxy group, C ₁-C ₁₅Alkylthio, C ₁-C ₁₅Silica-based, the C of alkane ₁-C ₁₅Alkyl siloxy, C ₂-C ₁₅Heterocyclic radical, replacement or unsubstituted C ₆-C ₁₅Aryl, replacement or unsubstituted C ₆-C ₁₅Aryloxy, connection C ₁-C ₁₅The carbonyl of alkyl, connection C ₆-C ₁₅The carbonyl of aryl, connection C ₂-C ₁₅The carbonyl of heterocyclic radical, connection replace or unsubstituted C ₁-C ₁₅The oxygen base carbonyl of saturated or unsaturated alkyl, connect C ₆-C ₁₅The carbonyl of aryloxy, connection C ₆-C ₁₅The carbonyl of heterocyclyloxy base, aminoacyl, connection replace or unsubstituted C ₁-C ₁₅Saturated or unsaturated alkyl is amino carbonyl, connection C ₆-C ₁₅The carbonyl of arylamino, connection C ₂-C ₁₅The carbonyl of heterocyclic radical amino, urea groups, replacement or unsubstituted C ₁-C ₁₅Alkyl urea groups, replacement or unsubstituted C ₆-C ₁₅Aryl-ureido, replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical urea groups, connection C ₁-C ₁₅The alkylsulfonyl of alkylamino, connection C ₆-C ₁₅The alkylsulfonyl of arylamino, connection C ₂-C ₁₅The alkylsulfonyl of heterocyclic radical amino; n ₁Be 10 ²-10 ⁴m ₁Be 10 ²-10 ⁴

Better, described high molecular polymer is in formula VIc, VId, VIe, VIIc, VIId, Poly-DCPD:

R ¹⁰, R ¹¹, R ¹², R ¹³And R ¹⁴Be hydrogen, halogen, replacement or unsubstituted C independently ₁-C ₈Alkyl, C ₁-C ₈Alkoxyl group, C ₁-C ₈Alkylthio, C ₁-C ₈Silica-based, the C of alkane ₁-C ₈Alkyl siloxy, C ₂-C ₈Heterocyclic radical, replacement or unsubstituted C ₆-C ₁₂Aryl, replacement or unsubstituted C ₆-C ₁₂Aryloxy, connection C ₁-C ₈The carbonyl of alkyl, connection C ₆-C ₁₂The carbonyl of aryl, connection C ₂-C ₈The carbonyl of heterocyclic radical, connection replace or unsubstituted C ₁-C ₈The oxygen base carbonyl of saturated or unsaturated alkyl, connect C ₆-C ₁₂The carbonyl of aryloxy, connection C ₆-C ₈The carbonyl of heterocyclyloxy base, aminoacyl, connection replace or unsubstituted C ₁-C ₈Saturated or unsaturated alkyl is amino carbonyl, connection C ₆-C ₁₂The carbonyl of arylamino, connection C ₂-C ₈The carbonyl of heterocyclic radical amino, connection C ₁-C ₈The alkylsulfonyl of alkylamino, connection C ₆-C ₁₂The alkylsulfonyl of arylamino, connection C ₂-C ₈The alkylsulfonyl of heterocyclic radical amino; n ₁Be 10 ²-10 ⁴m ₁Be 10 ²-10 ⁴

Best, described high molecular polymer is in formula VIc, VId, VIe, VIIc, VIId, Poly-DCPD:

Among the VIc:

A is CH ₂Or oxygen;

R ¹¹And R ¹⁰Alone for connecting C ₁-C ₃The oxygen base carbonyl of saturated or unsaturated alkyl, the C that connects non-replacement or replaced by CN ₆-C ₁₂The carbonyl of aryloxy, connection are by C ₆-C ₁₂The C that aryl replaces ₁-C ₃The carbonyl of alkoxyl group, connection are by C ₆-C ₁₂The C that the carbonyl of the alkoxyl group that aryloxy replaces, connection do not replace or CN replaces ₆-C ₁₂Aryloxy, connection C ₁-C ₃Saturated or carbonyl that unsaturated alkyl is amino, connect by C ₆The C that aryl replaces ₁-C ₃The carbonyl of alkylamino or connection C ₂-C ₅The carbonyl of heterocyclic radical;

Among the VIIc:

A is CH ₂, oxygen;

R ¹²Be C ₁-C ₅Saturated or undersaturated alkyl, by C ₁-C ₃The C that alkoxyl group replaces ₁-C ₃Alkyl, the C that is replaced by hydroxyl ₁-C ₃Alkyl, by C ₁-C ₃The C that alkyl acyloxy replaces ₁-C ₃Alkyl, by C ₆-C ₁₂The C that aryl replaces ₁-C ₃Alkyl, be connected C ₁-C ₃The C of the carbonyl substituted of alkoxyl group ₁-C ₃Alkyl, by C ₁-C ₃The C that carbalkoxy replaces ₆-C ₁₂Aryl, quilt

The aryl or the C that replace ₁-C ₃Alkoxyl group;

Among the VIId:

A is CH ₂Or oxygen;

R ¹⁴And R ¹³Be C ₁-C ₃Alkyl.

The invention still further relates to a kind of suc as formula the high molecular polymer shown in VIc, VId, VIe, VIIc, VIId and the Poly-DCPD, wherein, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, n ₁And m ₁As mentioned above.

Described high molecular polymer can be made by in following two kinds of methods any:

Method one: when raw material monomer was liquid, it comprised the following steps:

Under the protection of inert gas, raw material monomer and metal complex catalyst of the present invention carry out reacting by heating, can make VIc, VId, VIe, VIIc, VIId or Poly-DCPD.

Method two: when raw material monomer was solid or liquid, it comprised the following steps:

Under the protection of inert gas, in the anhydrous organic solvent, raw material monomer and metal complex catalyst of the present invention progressively are warming up to 75 ℃ of reactions from 20 ℃, can make VIc, VId, VIe, VIIc, VIId or Poly-DCPD.

In described method one: that catalyst consumption is preferable is the 0.5%-10% of raw material monomer molar weight, and what the temperature of reacting by heating was preferable is 30-120 ℃; In described method two: that catalyst consumption is preferable is the 0.01%-5% of raw material monomer molar weight, and that anhydrous organic solvent is preferable is ethylene dichloride (DCE).

When high molecular polymer was Poly-DCPD, it can be made by method one, and step is as follows:

Wherein, n ₁Be 10 ²-10 ⁴m ₁Be 10 ²-10 ⁴

In the luxuriant diene monomers of liquid dicyclo (DCPD), feed the argon gas oxygen of rushing, add the ruthenium catalyst (0.1-5 ‰) that this project etc. filters out again fast, the reacting by heating several minutes afterreaction liquid thick heat release that becomes sticky gradually between the 30-120 degree, last polymerization obtains the poly-luxuriant diene polymeric solid of dicyclo product (Poly-DCPD).Polymer P oly-DCPD solid have good hardness (＞80Gpa), modulus in flexure (＞20Gpa) and heat-drawn wire (＞200 ℃).

When high molecular polymer was VIc, it can be made by method two, and step is as follows:

1) under protection of inert gas, olefinic monomer raw material VIa is dissolved in the anhydrous solvent (as ethylene dichloride DCE), and argon filling is caught up with oxygen, adds the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, reaction is intensification (20-75 ℃) reacting by heating progressively, and reaction solution becomes sticky thick gradually;

2) after reaction is spent the night reaction solution slowly is poured in the ethanol and is precipitated out, after the suction filtration oven dry polymer solids product (VIc), productive rate is 80-98%; Wherein, R ¹⁰, R ¹¹, n ¹Definition with aforementioned.

The invention further relates to the application of high molecular polymer in effective carrier, tooth patching material, high molecule liquid crystal material, conductive polymer novel material, system film or the spinning material of the explosion-proof lamp for preparing high strength and high rigidity, tire material, polymer medicament prodrug.

Among the present invention, described alkyl is to comprise having the representative examples of saturated aliphatic alkyl of specifying carbonatoms purpose side chain or straight chain; As at " C ₁-C ₁₀Alkyl " in be defined as and be included in the group that has 1,2,3,4,5,6,7,8,9 or 10 carbon atom in straight chain or the branched structure.For example, " C ₁-C ₁₀Alkyl " specifically comprise methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, amyl group, hexyl, heptyl, octyl group, nonyl and decyl or the like.

Generation group after described " alkoxyl group " represented alkyl and Sauerstoffatom is connected, i.e. " RO-", R are alkyl.

Described " aryl " be meant any stable can be in each ring up to the monocycle or the bicyclic carbocyclic of 7 atoms, wherein at least one ring is an aromatic nucleus; The example of above-mentioned aryl unit comprises phenyl, naphthyl, tetralyl, 2,3-indanyl, xenyl, phenanthryl, anthryl or acenaphthenyl (acenaphthyl).Be appreciated that at aryl substituent be two ring substituents, and one of them ring is in the situation of non-aromatic ring, connection is undertaken by aromatic ring.

Can be in each ring of " heterocyclic aryl " expression up to the stable monocycle or two rings of 7 atoms, wherein at least one ring is aromatic nucleus and contains 1-4 heteroatoms that is selected from O, N and S; Heterocyclic aryl in this range of definition includes but not limited to: acridyl, carbazyl, cinnolines base, quinoxalinyl, pyrazolyl, indyl, benzotriazole base, furyl, thienyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl, oxazolyl, isoxazolyl, indyl, pyrazinyl, pyridazinyl, pyridyl, pyrimidyl, pyrryl, tetrahydroquinoline.As following heterocyclic definition, " heterocyclic aryl " it should also be understood that to be the N-oxide derivative that comprises any nitrogenous heteroaryl.The heterocyclic aryl substituting group is that two ring substituents and a ring are non-aromatic rings or do not comprise under the heteroatomic situation therein, is appreciated that connection carries out by aromatic ring or by the heteroatoms that comprises ring respectively.

Generation group after " alkylthio " represented alkyl and sulphur atom is connected, i.e. " RS-", R are alkyl.

Generation group after " aryloxy " represented aryl and Sauerstoffatom is connected, i.e. " RO-", R are aryl.

" virtue is amino " is meant " NH ₃" in the amino of a hydrogen after being replaced by aryl.

" alkyl imino " is meant the imino-that is connected with alkyl, and alkyl can be connected on the carbon of imino-or on the nitrogen; " alkyl imino of replacement " is meant the group after the one or more hydrogen in the alkyl imino are substituted.

" amino of replacement " is " NH ₃" in any one or a plurality of hydrogen group after being substituted.Substituting group can be C ₆-C ₂₀Aryl, formyl radical, C ₁-C ₂₀The C of alkyl acyl, replacement ₁-C ₂₀The C of alkyl acyl, alkyl sulphonyl, replacement ₁-C ₂₀Alkyl sulphonyl or the like.

Wherein, " alkyl sulphonyl " is the group that the sulphur atom on the alkylsulfonyl is connected with alkyl, and " alkyl sulphonyl of replacement " is that the one or more hydrogen in the alkyl sulphonyl are substituted the group after base replaces; The acyl group that " alkyl acyl " connecting alkyl for the carbon atom in the acyl group or nitrogen-atoms, " alkyl acyl of replacement " is substituted group after base replaces for any one or a plurality of hydrogen in the alkyl acyl.

" heterocyclic radical " is one or more fragrance or the nonaromatic heterocycles that contains in the heteroatoms that is selected from O, N and S, and comprises bicyclic groups.Therefore, " heterocyclic radical " comprise above-mentioned heterocyclic aryl with and dihydro or tetrahydrochysene analogue.Other example of " heterocyclic radical " includes but not limited to following: benzimidazolyl-; benzofuryl; the benzopyrazoles base; the benzotriazole base; benzothienyl benzoxazolyl; carbolinyl; furyl; imidazolyl; indolinyl; indyl; indazolyl; isobenzofuran-base; pseudoindolyl; isoquinolyl; isothiazolyl isoxazolyl oxazolyl oxazoline isoxazoline; the oxygen cyclobutyl; pyranyl; pyrazinyl; pyrazolyl; pyridazinyl; the pyridopyridine base; pyridazinyl; pyridyl; pyrimidyl; pyrryl; quinazolyl; quinolyl; quinoxalinyl; THP trtrahydropyranyl; thiadiazolyl group; thiazolyl; thienyl; triazolyl; azetidinyl; 1, the 4-alkyl dioxin; six hydrogen azatropylidene bases; piperazinyl; piperidyl; pyrrolidyl; morpholinyl; thio-morpholinyl; the dihydrobenzo imidazolyl; dihydro benzo furyl; the dihydrobenzo thienyl; Er hydrogen benzoxazolyl; the dihydrofuran base; the glyoxalidine base; indolinyl; the dihydro-isoxazole base; dihydro isothiazolyl Er Qing oxadiazole base dihydro-oxazole base; the dihydro pyrazinyl; the pyrazoline base; the dihydropyridine base; the dihydro-pyrimidin base; the pyrrolin base; the dihydroquinoline base; the dihydro tetrazyl; the thiodiazoline base; dihydro-thiazolyl; the dihydro-thiophene base; the dihydro triazolyl; the dihydro azetidinyl; the methylenedioxyphenyl formyl radical; tetrahydrofuran base and tetrahydro-thienyl and N-oxide compound thereof.Heterocyclic radical can be connected with central element through carbon atom or heteroatoms.

" heterocyclic radical of replacement " is substituted group after base replaces for any one or a plurality of hydrogen in the heterocyclic radical.

" alkyl formamides base " is the in succession group of alkyl of the carbon in the formamido-or nitrogen, and " the alkyl formamides base of replacement " is substituted group after base replaces for any one or a plurality of hydrogen in the alkyl formamides base.

" siloxy " is R for structural formula ₁R ₂R ₃The group of SiO-; " alkyl siloxy " is R ₁R ₂R ₃R among the SiO- ₁, R ₂And R ₃In have one at least for alkyl, all the other are the group of hydrogen; " alkyl siloxy of replacement "

Be the group of the one or more hydrogen in the alkyl siloxy after being substituted.

" alkyl formamides base " is the generation group after the hydrogen on the carbon or the hydrogen on the nitrogen are replaced by alkyl in the formamido-; " the alkyl formamides base of replacement " is that the one or more hydrogen in the alkyl formamides base are substituted the group after base replaces.

" alkane is silica-based " is structure R ₁R ₂R ₃Among the Si-, R ₁, R ₂And R ₃In have one at least for alkyl, all the other are the group of hydrogen.

" aminoacyl " for structural formula is

Group.

" carbonyl that connects alkylamino " connects the group that forms behind the alkyl for the nitrogen in the aminoacyl; " carbonyl of the connection alkylamino of replacement " is the group of the one or more hydrogen in the carbonyl that connects alkylamino after being substituted.

" alkyl urea groups " is the group after the one or more hydrogen on the nitrogen are replaced by alkyl in the urea groups; " the alkyl urea groups of replacement " is the group after the one or more hydrogen in the alkyl urea groups are substituted.

Raw material involved in the present invention and reagent is all commercially available getting except that specified otherwise.

Positive progressive effect of the present invention is:

1, the present invention passes through especially ruthenium complex of design and synthetic metal complex part and corresponding metal; fully the substituting group of research different ligands and the position of substitution thereof are to the influence of the catalytic activity and the stability of catalyzer; the result shows that metal complex catalyst of the present invention has the catalytic activity of higher olefin metathesis replacement(metathesis)reaction, and has catalytic activity and stability that adjacent alcoxyl vinylbenzene complex compound part that electron withdrawing groups such as amino-sulfonyl, sulfoamido, carbonyl, chlorine replace has obviously improved the respective metal complex compound.Metal complex catalyst of the present invention can be effective to intramolecular alkene ring closure reaction, intermolecular cycloolefin ring-opening polymerization etc., have industry using value widely, the field of waiting provides a kind of new synthetic method that passes through the olefin metathesis replacement(metathesis)reaction for new chemical materials and medicine are synthetic.

2, to design synthetic novel metal complexes structural formula be formula II a-II c in the present invention, the diversity selection of its chemical catalysis performance and physicals and application thereof increases significantly than the Grubbs-Hoveyda catalyzer and improves, and optimized the preparation method of metal complex, reduced preparation cost largely, for the industrialization production of the catalyzed reaction of metal complex provides an effective practical new.

3, the present invention has researched and developed high molecular polymer novel material by the different performance for preparing under the different monomer process conditions and preparation method thereof by the catalysis ring-opening polymerization of cycloolefin.

4, the main application of the high molecular polymer novel material of the present invention preparation is the novel materials such as effective novel vector, tooth patching material, high molecule liquid crystal material, conductive polymer of explosion-proof novel material, tire novel material, the polymer medicament prodrug of high strength and high rigidity, also can be used for making film and spinning prepares novel material.Can be development of human society in field of new how better product innovation is provided.

Embodiment:

The present invention is according to data (the patent US20070043180A1 of relevant olefin metathesis reaction catalyzer research and development, WO2007003135A1, WO96004289A1, WO97003096A1, US 20020107138A1, US 6921735 B2 and chemistry meeting magazine J.Am.Chem.Soc.1999,121,791-799, J.Am.Chem.Soc.2000,122,8168-8179), by dissimilar complex compound part (3a-3cz, 5a-5z, 7a-7t, 9a-9j, 11a-11j) complex reaction with the ruthenium complex intermediate has prepared dissimilar metal Ru complex compound (4a-4u, 6a-6v, 8a-8e, 10a-10e, 12a-12f), and the structure of having studied dissimilar complex compound parts by the catalytic cyclization and the ring-opening polymerization of alkene respectively and substituent effect are to the active influence of its respective metal complex catalysis, and furtherd investigate dissimilar metal complex catalysts and prepare the macromolecular material of different performance by the alkene ring-opening polymerization, and further high molecular polymer novel material and preparation method thereof and the multiple use that dissimilar novel complex compounds is used to prepare different performance optimized in research and development.

Below be to adopt the synthetic ruthenium complex 4a-4cz of complex compound part (3a-3cz) according to relevant documents and materials:

Below be the structural formula (1a:Cy=cyclohexyl, 1b:Mes=2,4,6-Three methyl Benzene) of complex compound 4a-4cz:

Below be the synthetic of ruthenium complex 4a-4cz:

Embodiment 1 ruthenium complex 4a's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3a (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4a, productive rate: 32% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4a) ¹HNMR (400MHz, CDCl ₃): δ 18.68 (s, Ru=CH), 7.23-6.65 (m, 10H, aromatic H), 6.36 (dd, J=2.8,9.6Hz, 1H, aromatic H), 6.03 (d, J=12.8Hz, 1H, NCH ₂), 4.14-3.90 (m, 4H, NCH ₂CH ₂N), 3.85 (s, 3H, OCH ₃), 3.47 (d, J=12.8Hz, 1H, NCH ₂), 2.89-1.62 (m, 18H, aromatic CH ₃).

Embodiment 2 ruthenium complex 4b's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3b (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4b, productive rate: 35% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4b) ¹HNMR (400MHz, CDCl ₃): δ 19.28 (d, J=8.4Hz, Ru=CH), 7.45 (d, J=8.8Hz, 2H, aromatic H), 7.31-7.16 (m, 3H, aromatic H), 6.83 (d, J=8.8Hz, 2H, aromatic H), 5.13 (t, J=12.4Hz, 1H, NH), 7.96 (d, J=12.4Hz, 1H, NCH ₂), 3.85 (d, J=12.4Hz, 1H, NCH ₂), 3.80 (s, 3H, OCH ₃), 2.28-1.24 (m, 33H, PCy ₃).

Embodiment 3 ruthenium complex 4c's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3c (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4c, productive rate: 14% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4c) ¹HNMR (400MHz, CDCl ₃): δ 18.99 (s, Ru=CH), 7.483-7.444 (m, 1H, aromatic H), 7.192-6.862 (m, 7H, aromatic H), 6.715-6.662 (m, 1H, aromatic H), 5.293 (t, J=13.2Hz, 1H, NHCH ₂), 4.19-3.58 (m, 8H, NHCH ₂, NCH ₂CH ₂N, NCH ₃), 2.52-2.37 (m, 18H, aromatic CH ₃).

Embodiment 4 ruthenium complex 4d's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3d (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4d, productive rate: 13% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4d) ¹HNMR (400MHz, CDCl ₃): δ 19.42 (d, J=8.8Hz, Ru=CH), 7.65 (d, J=9.2Hz, 2H, aromatic H), 7.35-7.17 (m, 3H, aromaticH), 6.93 (d, J=9.2Hz, 2H, aromatic H), 5.76 (d, J=12.4Hz, 1H, NH), 3.80 (s, 3H, OCH ₃), 3.70 (d, J=12.4Hz, 1H, NH), 2.57 (s, 3H, OCH ₃), 2.29-1.21 (m, 33H, PCy ₃).

Embodiment 5 ruthenium complex 4e's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3e (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4e, productive rate: 13% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4e) ¹HNMR (400MHz, CDCl ₃): δ 18.90 (s, Ru=CH), 7.21-7.15 (m, 1H, aromatic H), 7.05-6.94 (m, 5H, aromatic H), (6.87 m, 2H, aromatic H), 6.66-6.60 (m, 3H, aromatic H), 6.38 (dd, J=2.4,9.6Hz, 1H, aromatic H), 5.293 (t, J=13.2Hz, 1H, NHCH ₂), 4.19-3.55 (m, 8H, NHCH ₂, NCH ₂CH ₂N, NCH ₃), 2.86-2.10 (m, 18H, aromatic CH ₃).

Embodiment 6 ruthenium complex 4f's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3f (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4f, productive rate: 28% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4f) ¹HNMR (400MHz, CDCl ₃): δ 7.69-7.60 (m, 2H, aromatic H), 7.58-7.50 (m, 2H, aromatic H), 7.47-7.41 (m, 1H, aromatic H), 7.26-7.22 (m, 1H, aromatic H), (6.6.91-6.83 m, 2H, aromatic H), 5.32 (t, J=12.4Hz, 1H, NH), 4.97 (d, J=12.4Hz, 1H, NCH ₂), 3.87 (d, J=12.4Hz, 1H, NCH ₂), 3.78 (s, 3H, OCH ₃), 2.38-1.13 (m, 33H, PCy ₃).

Embodiment 7 ruthenium complex 4g's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3g (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4g, productive rate: 7% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4a) ¹HNMR (400MHz, CDCl ₃): δ 18.83 (s, Ru=CH), 7.51-7.49 (m, 1H, aromatic H), 7.17-7.06 (m, 5H, aromatic H), (6.95 m, 1H, aromatic H), 6.88 (m, 1H, aromatic H), 6.77 (m, 1H, aromatic H), 6.68-6.65 (m, 3H, aromatic H), 6.11 (d, J=12.8Hz, 1H, NCH ₂), 4.4-3.89 (m, 4H, NCH ₂CH ₂N), 3.83 (s, 3H, OCH ₃), 3.45 (d, J=12Hz, 1H, NCH ₂), 2.86-1.56 (m, 21H, NCH ₃, aromatic CH ₃).

Embodiment 8 ruthenium complex 4h's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3h (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4h, productive rate: 29% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4h) ¹HNMR (400MHz, CDCl ₃): δ 19.31 (d, J=8.4Hz, Ru=CH), 7.57-7.50 (m, 4H, aromatic H), 7.31-7.29 (m, 1H, aromatic H), 7.148 (d, J=5.6Hz, 1H, aromatic H), 6.84-6.81 (m, 2H, aromatic H), 5.78 (d, J=12Hz, 1H, NCH ₂), 3.71 (s, 3H, OCH ₃), 3.62 (d, J=12Hz, 1H, NCH ₂), 2.51 (s, 3H, NCH ₃), 2.22-1.13 (m, 33H, PCy ₃).

Embodiment 9 ruthenium complex 4j's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3j (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4j, productive rate: 37% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4j) ¹HNMR (400MHz, CDCl ₃): δ 18.83 (s, Ru=CH), 7.50-6.39 (m, 11H, aromatic H), 5.21 (t, J=12.4Hz, 1H, NH), 4.69-3.46 (m, 9H, NHCH ₂, NCH ₂CH ₂N, OCH ₃), 2.62-2.08 (m, 18H, aromatic CH ₃).

Embodiment 10 ruthenium complex 4k's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3k (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4k, productive rate: 52% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4k) ¹HNMR (400MHz, CDCl ₃): δ 19.35 (d, J=9.9Hz, Ru=CH), 8.11 (d, J=8.1Hz, 1H, aromatic H), 7.34-6.85 (m, 6H, aromaticH), 5.48 (d, J=12Hz, 1H, NCH ₂), 5.27 (t, J=6Hz, 1H, NH), 3.93 (d, J=12Hz, 1H, NCH ₂), 3.88 (s, 3H, OCH ₃), 2.33-1.24 (m, 33H, PCy ₃).

Embodiment 11 ruthenium complex 4m's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3m (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4m, productive rate: 84% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4m) ¹HNMR (400MHz, CDCl ₃): δ 18.89 (s, Ru=CH), 7.60-6.45 (m, 11H, aromatic H), 5.13-3.52 (m, 8H, NHCH ₂, NCH ₂CH ₂N, OCH), 2.95-2.10 (m, 18H, aromatic CH ₃), 0.95 (d, J=6.4Hz, 6H, OCH (CH ₃) ₂).

Embodiment 12 ruthenium complex 4n's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3n (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4n, productive rate: 58% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4n) ¹HNMR (400MHz, CDCl ₃): δ 19.55 (d, J=9.9Hz, Ru=CH), 8.14 (d, J=8.1Hz, 1H, aromatic H), 7.36-6.83 (m, 6H, aromaticH), 5.46 (d, J=12Hz, 1H, NCH ₂), 5.13 (t, J=6Hz, 1H, NH), 4.56 (m, 1H, OCH), 3.90 (d, J=12Hz, 1H, NCH ₂), 2.30-1.25 (m, 39H, PCy ₃).

Embodiment 13 ruthenium complex 4p's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3p (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4p, productive rate: 10% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4p) ¹HNMR (400MHz, CDCl ₃): δ 18.97 (s, Ru=CH), 7.50-6.58 (m, 11H, aromatic H), 5.26-3.52 (m, 8H, NHCH ₂, NCH ₂CH ₂N, OCH), 3.48-2.07 (m, 18H, aromatic CH ₃), 1.23 (d, J=6.4Hz, 6H, OCH (CH ₃) ₂).

Embodiment 14 ruthenium complex 4n's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3q (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4q, productive rate: 31% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4q) ¹HNMR (400MHz, CDCl ₃): δ 19.56 (d, J=9.9Hz, Ru=CH), 8.20 (d, J=8.1Hz, 1H, aromatic H), 7.66-6.84 (m, 6H, aromaticH), 5.46 (d, J=12Hz, 1H, NCH ₂), 5.22 (t, J=6Hz, 1H, NH), 4.56 (m, 1H, OCH), 3.95 (d, J=12Hz, 1H, NCH ₂), 2.34-0.87 (m, 39H, PCy ₃).

Embodiment 15 ruthenium complex 4r's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3r (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4r, productive rate: 14% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4n) ¹HNMR (400MHz, CDCl ₃): δ 18.91 (s, Ru=CH), 7.53-6.62 (m, 12H, aromatic H), 5.31 (t, J=12.4Hz, 1H, NH), 4.73-3.53 (m, 9H, NHCH ₂, NCH ₂CH ₂N, OCH ₃), 2.56-1.78 (m, 18H, aromatic CH ₃).

Embodiment 16 ruthenium complex 4s' is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3s (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4s, productive rate: 37% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4s) ¹HNMR (400MHz, CDCl ₃): δ 19.55 (d, J=9.9Hz, Ru=CH), 8.20 (d, J=8.1Hz, 1H, aromatic H), 7.64-6.86 (m, 7H, aromatic H), 5.52 (d, J=12Hz, 1H, NCH ₂), 5.35 (t, J=6Hz, 1H, NH), 3.96 (d, J=12Hz, 1H, NCH ₂), 3.91 (s, 3H, OCH ₃), 2.34-1.22 (m, 33H, PCy ₃).

Embodiment 17 ruthenium complex 4t's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3t (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid 4t with methyl alcohol or pentane-DCM washing then, and is impure, thick productive rate: 21%, do not have ¹The HNMR analytical results.

Embodiment 18 ruthenium complex 4u's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3u (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid 4u with methyl alcohol or pentane-DCM washing then, and is impure, thick productive rate: 7%, do not have ¹The HNMR analytical results.

Embodiment 19 ruthenium complex 4v's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3v (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4v, productive rate: 45% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4v) ¹HNMR (400MHz, CDCl ₃): δ 18.914 (s, Ru=CH), 7.535 (dd, J=1.2,8.0Hz, 1H, aromatic H), (7.225 m, 1H, aromatic H), 7.056-6.947 (m, 5H, aromatic H), (6.810 m, 1H, aromatic H), 6.712 (d, J=8.0Hz, 1H, aromatic H), 6.651 (t, J=7.6Hz, 1H, aromatic H), 6.462 (dd, J=2.4,9.6Hz, 1H, aromatic H), 5.198 (t, J=11.2Hz, 1H, NH), 4.658 (d, J=11.2Hz, 1H, NCH ₂), 4.180-3.857 (m, 6H, NCH ₂CH ₂N, OCH ₂), 3.549 (d, J=11.2Hz, 1H, NCH ₂), 2.790-2.000 (m, 18H, aromatic CH ₃), 1.19 (m, OCH ₂CH ₃).

Embodiment 20 ruthenium complex 4w's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3w (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4w, productive rate: 7% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4w) ¹HNMR (400MHz, CDCl ₃): δ 16.500 (s, Ru=CH), 7.680 (m, 1H, aromatic H), 7.099 (s, 4H, aromatic H), 6.984-6.800 (m, 6H, aromatic H), 4.650 (m, 1H, OCH), 4.229-4.178 (m, 6H, NCH ₂, NCH ₂CH ₂N), 3.884 (s, 3H, OCH ₃), 2.645 (s, 3H, NCH ₃), 2.495 (s, 12H, aromatic CH ₃), 2.347 (s, 6H, 18H, aromatic CH ₃), 0.912 (m, 6H, OCH (CH ₃) ₂).

Embodiment 21 ruthenium complex 4x's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3x (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4x, productive rate: 40% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4x) ¹HNMR (400MHz, CDCl ₃): δ 16.517 (s, Ru=CH), 7.580 (m, 1H, aromatic H), 7.094 (s, 4H, aromatic H), 6.925-6.597 (m, 6H, aromatic H), 4.521 (m, 1H, NH), 4.352 (s, 2H, NCH ₂), 4.180 (s, 4H, NCH ₂CH ₂N), 3.887 (s, 6H, OCH ₃), 2.494 (s, 12H, aromatic CH ₃), 2.402 (s, 6H, aromatic CH ₃).

Embodiment 22 ruthenium complex 4y's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3y (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4y, productive rate: 50% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4y) ¹HNMR (400MHz, CDCl ₃): δ 19.034 (s, Ru=CH), 8.376 (d, J=2.0Hz, 1H, aromatic H), 7.690 (d, J=1.6.0Hz, 1H, aromatic H), (7.437 d, J=7.6Hz, 1H, aromatic H), 7.206-7.029 (m, 5H, aromatic H), 6.834-6.590 (m, 3H, aromatic H), 5.240 (t, J=12Hz, 1H, NH), 4.660 (d, J=12Hz, 1H, NCH ₂), 4.451 (m, 1H, OCH ₃), 4.202-4.051 (m, 4H, NCH ₂CH ₂N), 3.615 (d, J=12Hz, 1H, NCH ₂), 2.692-2.026 (m, 18H, aromatic CH ₃), 1.177 (d, J=5.6Hz, 6H, OCH (CH ₃) ₂).

Embodiment 23 ruthenium complex 4z's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3z (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4z, productive rate: 49% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4z) ¹HNMR (400MHz, CDCl ₃): δ 16.524 (s, Ru=CH), 7.590 (m, 1H, aromatic H), 7.092 (s, 4H, aromatic H), 6.916-6.838 (m, 4H, aromatic H), 6.752-6.657 (m, 2H, aromatic H), 4.590 (m, 1H, NH, OCH), 4.347 (s, 2H, NCH ₂), 4.179 (s, 4H, NCH ₂CH ₂N), 3.886 (s, 3H, OCH ₃), 2.493 (s, 12H, aromatic CH ₃), 2.399 (s, 6H, 18H, aromatic CH ₃), 0.931 (m, 6H, OCH (CH ₃) ₂).

Embodiment 24 ruthenium complex 4aa's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3aa (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4aa, productive rate: 55% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4aa) ¹H-NMR (400MHz, CDCl ₃): δ 19.454 (d, J=9.6Hz, Ru=CH), 8.175 (d, J=7.6Hz, 1H, aromatic H), (7.397-7.325 m, 2H, aromatic H), 7.205-7.113 (m, 2H, aromatic H), (6.949-6.880 m, 2H, aromatic H), 5.523 (m, 1H, NCH ₂), 5.225 (m, 1H, NH), 4.159-3.942 (m, 3H, NCH ₂, OCH ₂), 2.358-0.812 (m, 36H, PCy ₃, OCH ₂CH ₃).

Embodiment 25 ruthenium complex 4ab's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3ab (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4ab, productive rate: 8% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4ab) ¹H-NMR (400MHz, CDCl ₃): δ 19.110 (s, 1H, Ru=CH), 8.364 (dd, J=2.0,8.0Hz, 1H, aromatic H), 7.289-6.646 (m, 10H, aromatic H), 5.303 (t, J=13.6Hz, 1H, NCH ₂), 4.226 (d, J=13.2Hz, 1H, NCH ₂), 4.104 (s, 3H, OCH ₃), 3.800 (s, 4H, NCH ₂CH ₂N), 3.686 (d, J=13.2Hz, 1H, NCH ₂), 2.646-2.075 (m, 18H, aromatic CH ₃).

Embodiment 26 ruthenium complex 4ac's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3ac (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4ac, productive rate: 63% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4ac) ¹H-NMR (400MHz, CDCl ₃): δ 17.370 (d, J=4.4Hz, Ru=CH), 7.740-7.674 (m, 2H, aromatic H), 7.111 (d, J=8.4Hz, aromaticH), 6.893-6.826 (m, 2H, aromatic H), (6.758-6.663 m, 2H, aromatic H), 4.656 (s, 1H, NH), 4.479 (s, 2H, NCH ₂), 4.334 (s, 3H, OCH ₃), 3.896 (s, 3H, OCH ₃), 2.345-1.272 (m, 33H, 18H, PCy ₃).

Embodiment 27 ruthenium complex 4ad's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3ad (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4ad, productive rate: 3% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4ad) ¹H-NMR (400MHz, CDCl ₃): δ 18.639 (s, 1H, Ru=CH), 7.542-7.470 (m, 2H, aromatic H), 7.287-7.692 (m, 10H, aromatic H), 5.513 (d, J=13.2Hz, 1H, NCH ₂), 4.152 (d, J=13.2Hz, 1H, NCH ₂), 4.083-3.769 (m, 7H, NCH ₂CH ₂N, OCH ₃), 3.195 (s, 3H, NCH ₃), 2.409 (m, 18H, aromatic CH ₃).

Embodiment 28 ruthenium complex 4ae's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3ae (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4ae, productive rate: 50% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4ae) ¹H-NMR (400MHz, CDCl ₃): δ 19.034 (s, 1H, Ru=CH), 8.376 (d, J=2.0Hz, 1H, aromatic H), 7.690 (d, J=1.6.0Hz, 1H, aromatic H), 7.437 (d, J=7.6Hz, 1H, aromatic H), 7.206-7.029 (m, 5H, aromaticH), 6.834-6.590 (m, 3H, aromatic H), 5.240 (t, J=12Hz, 1H, NH), 4.660 (d, J=12Hz, 1H, NCH ₂), 4.451 (m, 1H, OCH ₃), 4.202-4.051 (m, 4H, NCH ₂CH ₂N), 3.615 (d, J=12Hz, 1H, NCH ₂), 2.692-2.026 (m, 18H, aromatic CH ₃), 1.177 (d, J=5.6Hz, 6H, OCH (CH ₃) ₂).

Embodiment 29 ruthenium complex 4af's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3af (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4af, productive rate: 15% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4af) ¹H-NMR (400MHz, CDCl ₃): δ 18.541 (s, 1H, Ru=CH), 7.446 (d, J=8.0Hz, 1H, aromatic H), 7.239-7.191 (m, 4H, aromatic H), 7.058-6.958 (m, 6H, aromatic H), 6.143 (d, J=13.2Hz, 1H, NCH ₂), 5.393 (d, J=13.2Hz, 1H, NCH ₂), 4.074-3.770 (m, 7H, NCH ₂CH ₂N, OCH ₃), 3.518 (s, 3H, NCH ₃), 2.648-2.303 (m, 18H, aromatic CH ₃).

Embodiment 30 ruthenium complex 4ag's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3ag (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4ag, productive rate: 4% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4ag) ¹H-NMR (400MHz, CDCl ₃): δ 19.093 (s, 1H, Ru=CH), 7.514-6.701 (m, 13H, aromatic H), 5.310 (m, 1H, NH), 4.300 (d, J=12.9Hz, 1H, NCH ₂), 4.044 (s, 4H, NCH ₂CH ₂N), 3.612 (d, J=12.9Hz, 1H, NCH ₂), 2.452 (s, 12H, aromatic CH ₃), 2.332 (s, 6H, aromatic CH ₃).

Embodiment 31 ruthenium complex 4ah's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3ah (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4ah, productive rate: 5% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4ah) ¹H-NMR (400MHz, CDCl ₃): δ 19.093 (s, 1H, Ru=CH), 7.503-6.691 (m, 12H, aromatic H), 5.274 (m, 1H, NH), 4.330 (d, J=12.9Hz, 1H, NCH ₂), 4.043 (s, 4H, NCH ₂CH ₂N), 3.586 (d, J=12.9Hz, 1H, NCH ₂), 2.445 (s, 12H, aromatic CH ₃), 2.371 (s, 6H, aromatic CH ₃).

Embodiment 32 ruthenium complex 4am's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3am (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4am, productive rate: 40% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4am) ¹H-NMR (400MHz, CDCl ₃): δ 18.83 (s, 1H, Ru=CH), 7.36-6.14 (m, 10H, aromatic H), 5.12 (t, J=12.4Hz, 1H, NH), 4.50-3.42 (m, 12H, NHCH ₂, NCH ₂CH ₂N, OCH ₃), 2.62-2.05 (m, 18H, aromaticCH ₃).

Embodiment 33 ruthenium complex 4an's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3an (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4an, productive rate: 51% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4an) ¹H-NMR (400MHz, CDCl ₃): δ 18.90 (s, 1H, Ru=CH), 7.60-6.36 (m, 10H, aromatic H), 5.25 (t, J=12Hz, 1H, NH), 4.78 (d, J=12Hz, 1H, NCH ₂), 4.05 (s, 4H, NCH ₂CH ₂N), 3.53 (s, 3H, OCH ₃), 3.43 (d, J=12Hz, 1H, NCH ₂), 2.56-2.13 (m, 21H, aromatic CH ₃).

Embodiment 34 ruthenium complex 4ap's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3ap (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4ap, productive rate: 50% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4ap) ¹H-NMR (400MHz, CDCl ₃): δ 18.90 (s, 1H, Ru=CH), 7.38-6.37 (m, 9H, aromatic H), 4.85 (m, 2H, NH, NCH ₂), 3.99 (s, 4H, NCH ₂CH ₂N), 3.80 (d, J=12Hz, 1H, NCH ₂), 3.31 (s, 3H, OCH ₃), 2.69-0.85 (m, 38H, C (CH3) ₃, aromatic CH ₃).

Embodiment 35 ruthenium complex 4aq's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3aq (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4aq, productive rate: 37% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4aq) ¹H-NMR (400MHz, CDCl ₃): δ 19.08 (s, 1H, Ru=CH), 7.97-6.33 (m, 10H, aromatic H), 5.08 (m, 2H, NH, OCH), 4.34 (m, 1H, NCH ₂), 4.02 (s, 4H, NCH ₂CH ₂N), 3.41 (m, 1H, NCH ₂), 2.53-2.31 (m, 18H, aromatic CH ₃), 1.29 (s, 9H, C (CH3) ₃), 0.89-0.87 (m, 6H, OCH (CH ₃) ₂).

Embodiment 36 ruthenium complex 4ar's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3ar (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4ar, productive rate: 54% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4ar) ¹H-NMR (400MHz, CDCl ₃): δ 18.85 (s, 1H, Ru=CH), 7.26-6.07 (m, 10H, aromatic H), 5.04 (t, J=13.2Hz, 1H, NH), 4.48 (m, 1H, NCH ₂), 4.39-4.33 (m, 2H, OCH), 4.15-4.02 (m, 4H, NCH ₂CH ₂N), 3.65 (m, 1H, NCH ₂), 2.66-2.05 (m, 18H, aromatic CH ₃), 1.55 (m, 6H, OCH (CH ₃) ₂), 1.38 (m, 6H, OCH (CH ₃) ₂).

Embodiment 37 ruthenium complex 4as' is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3as (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4as, productive rate: 46% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4as) ¹H-NMR (400MHz, CDCl ₃): δ 18.98 (s, 1H, Ru=CH), 7.66-6.39 (m, 10H, aromatic H), 5.17 (t, J=13.2Hz, 1H, NH), 4.71 (d, J=13.2Hz, 1H, NCH ₂), 4.36 (m, 1H, OCH), 4.06 (brs, 4H, NCH ₂CH ₂N), 3.42 (d, J=13.2Hz, 1H, NCH ₂), 2.63-2.09 (m, 21H, aromatic CH ₃), 1.09 (m, 6H, OCH (CH ₃) ₂).

Embodiment 38 ruthenium complex 4at's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3at (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4at, productive rate: 37% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4at) ¹H-NMR (400MHz, CDCl ₃): δ 19.46 (d, J=9.9Hz, Ru=CH), 8.15 (d, J=8.1Hz, 1H, aromatic H), 7.33-7.13 (m, 3H, aromaticH), 6.46 (m, 2H, aromatic H), 5.26 (m, 2H, NCH ₂), 3.79 (s, 3H, OCH ₃), 3.76 (s, 3H, OCH ₃), 2.26-1.25 (m, 33H, PCy ₃).

Embodiment 39 ruthenium complex 4aw's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3aw (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4aw, productive rate: 8% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4aw) ¹H-NMR (400MHz, CDCl ₃): δ 19.43 (d, J=9.9Hz, Ru=CH), 8.57 (d, J=8.1Hz, 1H, aromatic H), 7.26-6.78 (m, 5H, aromaticH), 5.29 (m, 2H, OCH, NH), 4.53 (m, 1H, NCH ₂), 3.72 (m, 1H, NCH ₂), 2.26-1.24 (m, 48H, PCy ₃, C (CH3) ₃, OCH (CH ₃) ₂).

Embodiment 40 ruthenium complex 4az's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3az (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4az, productive rate: 31% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4az) ¹H-NMR (400MHz, CDCl ₃): δ 18.53 (s, 1H, Ru=CH), 7.26-5.75 (m, 10H, aromatic H), 4.88 (d, J=11.2Hz, 1H, NCH ₂), 4.52-4.43 (m, 2H, OCH), 4.14-3.88 (m, 5H, NCH ₂, NCH ₂CH ₂N), 2.98-1.39 (m, 27H, NCH ₃, aromatic CH ₃, OCH (CH ₃) ₂).

Embodiment 41 ruthenium complex 4ba's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3ba (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4ba, productive rate: 44% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4ba) ¹H-NMR (400MHz, CDCl ₃): δ 18.99 (s, 1H, Ru=CH), 7.45-6.36 (m, 9H, aromatic H), 5.05 (m, 2H, OCH, NH), 3.98-3.91 (m, 5H, NCH ₂, NCH ₂CH ₂N), 3.72 (d, J=13.2Hz, 1H, NCH ₂), 2.48-2.34 (m, 19H, C (CH3) ₃, aromatic CH ₃), 1.45-0.95 (m, 21H, OCH (CH ₃) ₂, C (CH3) ₃).

Embodiment 42 ruthenium complex 4bb's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3bb (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4bb, productive rate: 42% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4bb) ¹H-NMR (400MHz, CDCl ₃): 19.02 (s, 1H, Ru=CH), 7.21-6.82 (m, 8H, aromatic H), 6.40 (dd, J=9.6Hz, 1.6Hz, aromaticH), 5.206 (m, 1H, NH), 4.06-4.00 (m, 5H, NCH ₂, NCH ₂CH ₂NH), 3.7 (s, 3H, OCH ₃), 3.54 (d, J=13.2Hz, 1H, NCH ₂), 2.48-2.18 (m, 24H, aromatic CH ₃).

Embodiment 43 ruthenium complex 4be's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3be (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4be, productive rate: 48% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4be) ¹H-NMR (400MHz, CDCl ₃): δ 18.88 (s, 1H, Ru=CH), 7.57-6.44 (m, 11H, aromatic H), 5.36 (t, J=13.2Hz, 1H, NH), 4.16-4.02 (m, 5H, NCH ₂, NCH ₂CH ₂N), 4.01 (d, J=13.2Hz, 1H, NCH ₂), 2.75-2.00 (m, 19H, CH (CH ₃) ₂, aromatic CH ₃), 1.01-0.90 (m, 6H, CH (CH3) ₂).

Embodiment 44 ruthenium complex 4bg's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3bg (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4bg, productive rate: 52% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4bg) ¹H-NMR (400MHz, CDCl ₃): δ 18.95 (s, 1H, Ru=CH), 7.43-6.36 (m, 10H, aromatic H), 4.00 (m, 6H, NCH ₂, NCH ₂CH ₂N), 2.67-2.06 (m, 20H, CH (CH ₃) ₂, aromatic CH ₃), 0.90-0.83 (m, 12H, CH (CH3) ₂).

Embodiment 45 ruthenium complex 4bj's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3bj (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4bj, productive rate: 64% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4bj) ¹H-NMR (400MHz, CDCl ₃): δ 18.88 (s, 1H, Ru=CH), 7.25-6.36 (m, 9H, aromatic H), 5.40 (t, J=13.2Hz, 1H, NH), 4.14-4.00 (m, 6H, NCH ₂, NCH ₂CH ₂N), 2.77-1.90 (m, 27H, aromatic CH ₃).

Embodiment 46 ruthenium complex 4bk's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3bk (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4bk, productive rate: 26% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4bk) ¹H-NMR (400MHz, CDCl ₃): δ 18.91 (s, 1H, Ru=CH), 7.63-6.42 (m, 10H, aromatic H), 5.27 (t, J=13.2Hz, 1H, NH), 4.13-4.01 (m, 5H, NCH ₂, NCH ₂CH ₂N), 3.44 (d, J=13.2Hz, 1H, NCH ₂), 2.46-2.00 (m, 21H, aromatic CH ₃).

Embodiment 47 ruthenium complex 4bn's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3bn (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4bn, productive rate: 38% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4bn) ¹H-NMR (400MHz, CDCl ₃): δ 18.75 (s, 1H, Ru=CH), 7.26-6.21 (m, 9H, aromatic H), 4.05-3.85 (m, 5H, NCH ₂, NCH ₂CH ₂N), 3.72 (s, 3H, OCH ₃), 3.34 (d, J=13.2Hz, 1H, NCH ₂), 2.82-0.95 (m, 30H, NCH ₃, aromatic CH ₃).

Embodiment 48 ruthenium complex 4br's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3br (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4br, productive rate: 14% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4br) ¹H-NMR (400MHz, CDCl ₃): δ 18.89 (s, 1H, Ru=CH), 7.69-6.43 (m, 10H, aromatic H), 5.23 (dd, J=13.2,11.3Hz, 1H, NH), 4.16-3.94 (m, 5H, NCH ₂, NCH ₂CH ₂N), 3.46 (d, J=11.3Hz, 1H, NCH ₂), 2.62-1.00 (m, 21H, aromatic CH ₃).

Embodiment 49 ruthenium complex 4bs' is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3bs (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4bs, productive rate: 17% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4bs) ¹H-NMR (400MHz, CDCl ₃): δ 19.53 (d, J=9.9Hz, Ru=CH), 8.43 (d, J=8.1Hz, 1H, aromatic H), 7.57-6.79 (m, 5H, aromaticH), 5.43 (dd, J=13.2,11.3Hz, 1H, NH), 4.60 (d, J=13.2Hz, 1H, NCH ₂), 3.72 (d, J=11.3Hz, 1H, NCH ₂), 2.29-0.95 (m, 36H, PCy ₃, aromatic CH ₃).

Embodiment 50 ruthenium complex 4bv's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3bv (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4bv, productive rate: 90% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4bv) ¹H-NMR (400MHz, CDCl ₃): δ 18.75 (s, 1H, Ru=CH), and 7.50-7.44 (m, 2H, aromatic H), 7.04-6.36 (m, 9H, aromatic H), 5.32-5.21 (m, 1H, NH), 4.65 (d, J=13.2Hz, 1H, NCH ₂), 4.16-4.04 (m, 4H, NCH ₂CH ₂N), 3.59 (s, 3H, OCH ₃), 3.48 (d, J=13.2Hz, 1H, NCH ₂), 2.62-2.32 (m, 18H, aromatic CH ₃).

Embodiment 51 ruthenium complex 4bw's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3bw (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4bw, productive rate: 49% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4bw) ¹H-NMR (400MHz, CDCl ₃): δ 19.39 (d, J=10Hz, Ru=CH), and 8.11 (d, J=8Hz, 1H, aromatic H), 7.64-7.06 (m, 2H, aromatic H), 7.16-6.87 (m, 4H, aromatic H), 5.47 (m, 1H, NH), 5.24 (m, 1H, NCH ₂), 3.92 (d, J=13.6Hz, 1H, NCH ₂), 3.80 (s, 3H, OCH ₃), 2.30-0.87 (m, 33H, PCy ₃).

Embodiment 52 ruthenium complex 4bx's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3bx (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4bx, productive rate: 65% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4bx) ¹H-NMR (300MHz, CDCl3): δ 18.82 (s, 1H, Ru=CH), and 7.47-7.43 (m, 2H, aromatic H), 7.01-6.56 (m, 9H, aromatic H), 5.12-5.09 (m, 1H, NH), 4.56-4.45 (m, 2H, OCH, NHCH ₂), 4.40-4.15 (m, 4H, NCH ₂CH ₂N), 3.48-3.45 (m, 1H, NHCH ₂), 2.64-2.04 (m, 18H, aromatic CH ₃), 1.10 (d, J=6.4Hz, 6H, OCH (CH ₃) ₂).

Embodiment 53 ruthenium complex 4cc's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cc (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cc, productive rate: 23% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4cc) ¹H-NMR (300MHz, CDCl3): δ 18.97 (s, 1H, Ru=CH), and 8.54-8.45 (m, 2H, aromatic H), 6.66-6.96 (m, 8H, aromatic H), 4.16-4.10 (m, 1H, NH), 4.03 (s, 4H, NCH ₂CH ₂N), 2.63-1.75 (m, 22H, NHCH ₂, aromatic CH ₃), 0.92 (d, J=7.6Hz, OCH (CH ₃) ₂), 0.83 (d, J=7.6Hz, OCH (CH ₃) ₂).

Embodiment 54 ruthenium complex 4cd's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cd (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cd, productive rate: 42% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4cd) ¹H-NMR (400MHz, CDCl ₃): δ 19.02 (s, 1H, Ru=CH), 7.87 (dd, J=8,1.2Hz, 1H, aromatic H), (7.44 dd, J=7.2,1.2Hz, 1H, aromatic H), 7.25-7.03 (m, 9H, aromatic H), and 5.37-5.30 (m, 1H, NH), 4.76-4.74 (m, 1H, NCH ₂), 4.16-4.01 (m, 4H, NCH ₂CH ₂N), 3.58-3.54 (m, 4H, NCH ₂, OCH ₃), 2.75 (s, 6H, NCH ₃), 2.73-1.98 (m, 18H, aromatic CH ₃).

Embodiment 55 ruthenium complex 4cf's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cf (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cf, productive rate: 32% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4cf) ¹H-NMR (300MHz, CDCl3): δ 19.03 (s, 1H, Ru=CH), 7.48-6.63 (m, 10H, aromatic H), 5.53 (m, 1H, NH), 4.81-4.78 (m, 1H, NHCH ₂), 4.00 (s, 4H, NCH ₂CH ₂N), 2.51-2.49 (m, 1H, NHCH ₂), 2.51-2.32 (m, 18H, aromatic CH ₃), 1.12 (d, J=7.6Hz, OCH (CH ₃) ₂), 1.04 (d, J=7.6Hz, OCH (CH ₃) ₂).

Embodiment 56 ruthenium complex 4cg's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cg (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cg, productive rate: 51% with methyl alcohol or pentane-DCM washing then.

After testing, ¹H-NMR (300MHz, CDCl3): δ 19.06 (s, 1H, Ru=CH), 7.87 (d, J=7.6Hz, 1H, aromatic H), 7.42 (d, J=7.6Hz, 1H, aromatic H), 7.29 (d, J=12Hz, 1H, aromatic H), 7.11-6.56 (m, 8H, aromatic H), 5.22-5.19 (m, 1H, NH), 4.63-4.64 (m, 1H, NHCH ₂), 4.45-4.42 (m, 1H, OCH), 4.14-4.01 (m, 4H, NCH ₂CH ₂N), 3.56-3.53 (m, 1H, NHCH ₂), 3.12-3.07 (m, 4H, NCH ₂), 2.67-2.36 (m, 18H, aromatic CH ₃), 1.99-1.00 (m, 24H, CH ₂CH ₂CH ₂CH ₃, OCH (CH ₃) ₂).

Embodiment 57 ruthenium complex 4ch's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3ch (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4ch, productive rate: 74% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4ch) ¹H-NMR (300MHz, CDCl3): δ 19.06 (s, 1H, Ru=CH), 7.87 (d, J=7.6Hz, 1H, aromatic H), 7.42 (d, J=7.6Hz, 1H, aromaticH), 7.11-6.56 (m, 9H, aromatic H), and 5.27-5.20 (m, 1H, NH), 4.64-4.61 (m, 1H, NHCH ₂), 4.46-4.44 (m, 1H, OCH), 4.14-4.01 (m, 4H, NCH ₂CH ₂N), 3.59-3.56 (m, 1H, NHCH ₂), 3.12-3.07 (m, 4H, NCH ₂), 2.75 (s, 6H, NCH ₃), 2.67-2.36 (m, 18H, aromatic CH ₃), 1.13 (d, J=6.0Hz, 6H, OCH (CH ₃) ₂).

Embodiment 58 ruthenium complex 4cj's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cj (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cj, productive rate: 77% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4cj) ¹H-NMR (400MHz, CDCl ₃): δ 19.56 (d, J=9.6Hz, Ru=CH), 8.21 (d, J=8.0Hz, 1H, aromatic H), 8.09 (d, J=2Hz, 1H, aromatic H), 8.10 (dd, J=7.6,2Hz, 1H, aromatic H), 7.34-6.87 (m, 4H, aromaticH), 5.47-5.44 (m, 1H, NH), 5.33-5.27 (m, 1H, NCH ₂), 4.62-4.56 (m, 1H, OCH), 3.99-3.96 (m, 1H, NCH ₂), 2.80 (s, 6H, NCH ₃), 2.30-1.24 (m, 39H, PCy ₃, OCH (CH ₃) ₂).

Embodiment 59 ruthenium complex 4ck's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3ck (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4ck, productive rate: 47% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4ck) ¹H-NMR (400MHz, CDCl ₃): δ 18.99 (s, 1H, Ru=CH), 7.88 (dd, J=8,2Hz, 1H, aromatic H), (7.44 dd, J=7.2,1.2Hz, 1H, aromatic H), 7.28-6.63 (m, 9H, aromatic H), and 5.35-5.28 (m, 1H, NH), 4.75-4.72 (m, 1H, NCH ₂), 4.16-4.12 (m, 4H, NCH ₂CH ₂N), 3.61 (s, 3H, OCH ₃), 3.56-3.52 (m, 4H, NCH ₂), 3.10-3.06 (m, 4H, NCH ₂), 2.63-2.05 (m, 18H, aromatic CH ₃), 1.37-0.98 (m, 14H, CH ₂CH ₂CH ₃).

Embodiment 60 ruthenium complex 4cm's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cm (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cm, productive rate: 27% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4cm) ¹H-NMR (400MHz, CDCl ₃): δ 19.03 (s, 1H, Ru=CH), 7.60 (d, J=7.6Hz, 1H, aromatic H), 7.43 (d, J=3.6Hz, 1H, aromaticH), 7.14 (s, 1H, aromatic H), (7.09-7.00 m, 5H, aromatic H), 6.81-6.57 (m, 3H, aromatic H), 5.22 (m, 1H, NH), 4.64-4.61 (m, 1H, NCH ₂), 4.64-4.42 (m, 2H, OCH, NH), 4.15-4.02 (m, 4H, NCH ₂CH ₂N), 3.16 (m, 1H, NCH ₂), 3.17 (m, 1H, NCH), 2.67-2.00 (m, 18H, aromatic CH ₃), 1.85-1.00 (m, 16H, CH ₂CH ₂, OCH (CH ₃) ₂).

Embodiment 61 ruthenium complex 4cn's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cn (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cn, productive rate: 26% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4cn) ¹H-NMR (400MHz, CDCl ₃): δ 18.96 (s, 1H, Ru=CH), 7.95 (d, J=7.6Hz, 1H, aromatic H), 7.45 (d, J=8Hz, 1H, aromatic H), 7.35 (s, 1H, aromatic H), (7.07-7.03 m, 5H, aromatic H), 6.78-6.65 (m, 3H, aromatic H), 5.31 (m, 1H, NH), 4.76-4.73 (m, 1H, NCH ₂), 4.38-4.37 (m, 1H, NH), 4.14-4.03 (m, 4H, NCH ₂CH ₂N), 3.60 (s, 3H, OCH ₃), 3.56-3.53 (m, 1H, NCH ₂), 3.14-3.13 (m, 1H, NCH), 2.66-1.27 (m, 34H, aromatic CH ₃, CH ₂CH ₂, OCH (CH ₃) ₂).

Embodiment 62 ruthenium complex 4cp's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cp (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cp, productive rate: 68% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4cp) ¹H-NMR (400MHz, CDCl ₃): δ 18.90 (s, 1H, Ru=CH), and 7.27-6.77 (m, 9H, aromatic H), 6.41 (d, J=8.0Hz, 1H, aromatic H), 5.43 (t, J=13.2Hz, 1H, NH), 4.18-4.00 (m, 5H, NCH ₂, NCH ₂CH ₂N), 3.25 (d, J=13.6Hz, NCH ₂), 2.76-1.27 (m, 24H, aromatic CH ₃).

Embodiment 63 ruthenium complex 4cr's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cr (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cr, productive rate: 59% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4cr) ¹H-NMR (400MHz, CDCl ₃): δ 18.82 (s, 1H, Ru=CH), 8.15 (dd, J=6.4,1.2Hz, 2H, aromaticH), 7.51 (d, J=1.2Hz, 1H, aromatic H), (7.44 d, J=1.2Hz, 1H, aromatic H), 7.05-6.99 (m, 5H, aromatic H), 8.15 (d, J=6.4Hz, 2H, aromatic H), 6.59-6.56 (m, 1H, aromatic H), 5.22 (m, 1H, NH), 4.63 (m, 1H, NHCH ₂), 4.41 (m, 1H, OCH), 3.96 (m, 4H, NCH ₂CH ₂N), 3.55-3.52 (m, 1H, NHCH ₂), 2.66-2.33 (m, 18H, aromatic CH ₃), 1.14 (d, J=6.4Hz, 6H, OCH (CH ₃) ₂).

Embodiment 64 ruthenium complex 4cs' is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cs (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cs, productive rate: 82% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4cs) ¹H-NMR (400MHz, CDCl ₃): δ 18.73 (s, 1H, Ru=CH), 7.45-6.60 (m, 7H, aromatic H), 6.44 (dd, J=8.0,1.2Hz, 1H, aromaticH), 6.38 (dd, J=7.6,2.4Hz, 1H, aromatic H), 5.06 (m, 1H, NH), 4.17-3.92 (m, 7H, NCH ₂, NCH ₂CH ₂N, OCH ₂), 3.55 (m, 1H, NCH ₂), 2.44-1.00 (m, 7H, aromaticCH ₃).

Embodiment 65 ruthenium complex 4ct's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3ct (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4ct, productive rate: 57% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4ct) ¹H-NMR (400MHz, CDCl ₃): δ 19.40 (d, J=10Hz, Ru=CH), 7.40 (d, J=7.6Hz, 1H, aromatic H), 7.31-7.29 (m, 2H, aromaticH), 7.26 (dd, J=7.6,2Hz, 1H, aromatic H), 6.84-6.82 (m, 2H, aromatic H), 5.15 (m, 1H, NH), 4.93 (m, 1H, NCH ₂), 3.96-3.83 (m, 3H, OCH ₂, NCH ₂), 2.28-1.00 (m, 40H, PCy ₃, CH ₂CH ₂CH ₃).

Embodiment 66 ruthenium complex 4cu's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cu (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cu, productive rate: 65% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4cu) ¹H-NMR (400MHz, CDCl ₃): δ 18.68 (s, 1H, Ru=CH), 7.28-6.96 (m, 10H, aromatic H), 6.37 (d, J=8.5Hz, 1H, aromatic H), 5.31 (m, 3H, NCH ₂, OCH ₂), 4.71-4.01 (m, 5H, NH, NCH ₂CH ₂N), 3.58 (d, J=12.8Hz, 1H, NCH ₂), 2.89-1.29 (m, 21H, OCH ₂CH ₃, aromatic CH ₃).

Embodiment 67 ruthenium complex 4cw's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cw (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cw, productive rate: 85% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4cw) ¹H-NMR (400MHz, CDCl ₃): δ 18.68 (s, 1H, Ru=CH), 7.28-6.42 (m, 10H, aromatic H), 6.37 (d, J=8.5Hz, 1H, aromatic H), 5.05 (m, 1H, NCH ₂), 4.06-3.93 (m, 7H, NH, NCH ₂CH ₂N, OCH ₂), 3.57 (d, J=12.8Hz, 1H, NCH ₂), 2.89-1.29 (m, 29H, CH ₂CH ₃, aromatic CH ₃).

Embodiment 68 ruthenium complex 4cy's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cy (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cy, productive rate: 70% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4cy) ¹H-NMR (400MHz, CDCl ₃): δ 18.68 (s, 1H, Ru=CH), 7.28-6.61 (m, 10H, aromatic H), 6.41 (d, J=8.5Hz, 1H, aromatic H), 5.05 (m, 1H, NCH ₂), 4.52-4.06 (m, 6H, NH, NCH ₂CH ₂N, OCH), 3.57 (d, J=12.8Hz, 1H, NCH ₂), 2.89-1.29 (m, 24H, CH ₂CH ₃, aromatic CH ₃).

Embodiment 69 ruthenium complex 4cz's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 3cz (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 4cz, productive rate: 64% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (4cz) ¹H-NMR (400MHz, CDCl ₃): δ 19.28 (d, J=8.4Hz, Ru=CH), 7.46 (d, J=8.8Hz, 2H, aromatic H), 7.40-7.18 (m, 3H, aromaticH), 6.84 (d, J=8.8Hz, 2H, aromatic H), 5.21 (t, J=12.4Hz, 1H, NH), 4.93 (d, J=12.4Hz, 1H, NCH ₂), 4.50 (m, 1H, OCH), 3.90-3.86 (m, 1H, NCH ₂), 2.30-1.21 (m, 39H, CH ₂CH ₃, PCy ₃).

Below be to adopt the synthetic ruthenium complex 6a-6z of complex compound part (5a-5z) according to relevant documents and materials:

Below be the structural formula (1a:Cy=cyclohexyl, 1b:Mes=2,4,6-Three methyl Benzene) of complex compound 6a-6z:

Embodiment 70 ruthenium complex 6a's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5a (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6a, productive rate: 79% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6a) ¹HNMR (400MHz, CDCl ₃): δ 18.529 (s, 1H, Ru=CH), 8.587 (s, 1H, N=CH), 7.283-6.490 (m, 11H, aromatic H), 4.160 (s, 4H, NCH ₂CH ₂N), 2.50 (s, 12H, aromatic CH ₃), 2.42 (s, 6H, aromatic CH ₃).

Embodiment 71 ruthenium complex 6b's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5b (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6b, productive rate: 77% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6a) ¹HNMR (400MHz, CDCl ₃): δ 19.197 (d, J=10.8Hz, Ru=CH), 8.819 (d, J=9.2Hz, 1H, N=CH), (7.835 m, 1H, aromatic H), 7.795 (d, J=8.4Hz, 1H, aromatic H), (7.453 m, 4H, aromatic H), 2.459-1.291 (m, 33H, PCy ₃).

Embodiment 72 ruthenium complex 6c's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5c (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6c, productive rate: 96% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6c) ¹HNMR (400MHz, CDCl ₃): δ 18.516 (s, 1H, Ru=CH), 8.599 (s, 1H, N=CH), 7.283-7.133 (m, 7H, aromatic H), 7.017 (d, J=8.8Hz, 1H, aromatic H), 6.800 (m, 1H, aromatic H), (6.091 d, J=8.8Hz, 1H, aromatic H), 4.160 (s, 4H, NCH ₂CH ₂N), 3.837 (s, 3H, OCH ₃), 2.514 (m, 18H, aromatic CH ₃).

Embodiment 73 ruthenium complex 6d's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5d (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6d, productive rate: 65% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6d) ¹HNMR (400MHz, CDCl ₃): δ 19.639 (d, J=11.6Hz, Ru=CH), 8.868 (d, J=13.6Hz, 1H, N=CH), 7.865-7.842 (m, 3H, aromaticH), 7.430-7.97 (m, 2H, aromatic H), (6.999-6.976 m, 2H, aromatic H), 3.768 (s, 3H, OCH ₃), 2.310-1.074 (m, 33H, PCy ₃).

Embodiment 74 ruthenium complex 6e's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5e (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6e, productive rate: 31% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6e) ¹HNMR (400MHz, CDCl ₃): δ 18.731 (s, 1H, Ru=CH), 8.619 (s, 1H, N=CH), 7.670-7.456 (m, 3H, aromatic H), 7.113 (s, 4H, aromatic H), 6.779-6.651 (m, 5H, aromatic H), 4.131 (s, 4H, NCH ₂CH ₂N), 3.810 (s, 3H, OCH ₃), 2.493 (m, 18H, aromatic CH ₃).

Embodiment 75 ruthenium complex 6f's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5f (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6f, productive rate: 7% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6f) ¹HNMR (400MHz, CDCl ₃): δ 19.373 (d, J=11.7Hz, Ru=CH), 8.836 (d, J=9.3Hz, 1H, N=CH), 7.877-7.682 (m, 6H, aromatic H), 6.974 (d, J=8.7Hz, 2H, aromatic H), 3.885 (s, 3H, OCH ₃), 2.496-1.275 (m, 33H, PCy ₃).

Embodiment 76 ruthenium complex 6g's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5g (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6g, productive rate: 24% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6g) ¹HNMR (400MHz, CDCl ₃): δ 18.741 (s, 1H, Ru=CH), 8.602 (s, 1H, N=CH), 7.692-7.485 (m, 3H, aromatic H), 7.120-7.042 (m, 8H, aromatic H), 6.798 (d, J=8.7Hz, 1H, aromatic H), 4.131 (s, 4H, NCH ₂CH ₂N), 2.495 (m, 18H, aromatic CH ₃).

Embodiment 77 ruthenium complex 6h's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5h (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6h, productive rate: 27% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6h) ¹HNMR (400MHz, CDCl ₃): δ 18.95 (d, J=6.4Hz, Ru=CH), 10.26 (d, J=9.2Hz, 1H, N=CH), 7.985-7.256 (m, 8H, aromatic H), 2.430-0.854 (m, 33H, PCy ₃).

Embodiment 78 ruthenium complex 6j's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5j (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6j, productive rate: 38% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6j) ¹HNMR (400MHz, CDCl ₃): δ 18.751 (s, 1H, Ru=CH), 8.647 (s, 1H, N=CH), 7.710-6.789 (m, 13H, aromatic H), 4.197 (s, 4H, NCH ₂CH ₂N), 2.490 (m, 18H, aromatic CH ₃).

Embodiment 79 ruthenium complex 6k's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5k (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6k, productive rate: 15% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6k) ¹HNMR (400MHz, CDCl ₃): δ 19.45 (d, J=6.4Hz, Ru=CH), 8.868 (d, J=9.3Hz, 1H, N=CH), 7.896-7.259 (m, 9H, aromatic H), 2.491-1.268 (m, 33H, PCy ₃).

Embodiment 80 ruthenium complex 6m's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5m (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6m, productive rate: 17% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6m) ¹HNMR (400MHz, CDCl ₃): δ 18.595 (s, 1H, Ru=CH), 8.579 (s, 1H, N=CH), 7.480-7.292 (m, 2H, aromatic H), 7.016 (d, J=8.8Hz, 2H, aromatic H), 6.743-6.687 (m, 3H, aromatic H), 4.165 (s, 4H, NCH ₂CH ₂N), 3.845 (s, 3H, OCH ₃), 2.519 (m, 18H, aromatic CH ₃).

Embodiment 81 ruthenium complex 6n's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5n (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6n, productive rate: 40% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6n) ¹HNMR (400MHz, CDCl ₃): δ 18.522 (s, 1H, Ru=CH), 8.592 (s, 1H, N=CH), 7.292-6.838 (m, 10H, aromatic H), 6.838-6.818 (m, 1H, aromatic H), 4.167 (s, 4H, NCH ₂CH ₂N), 2.517 (m, 18H, aromatic CH ₃).

Embodiment 82 ruthenium complex 6p's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5p (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6p, productive rate: 47% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6p) ¹HNMR (400MHz, CDCl ₃): δ 19.214 (d, J=11.2Hz, Ru=CH), 8.819 (d, J=9.2Hz, 1H, N=CH), 7.893-7.858 (m, 3H, aromatic H), 7.507-7.416 (m, 4H, aromatic H), 2.501-1.573 (m, 33H, PCy ₃).

Embodiment 83 ruthenium complex 6q's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5q (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6q, productive rate: 33% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6q) ¹HNMR (400MHz, CDCl ₃): δ 18.541 (s, 1H, Ru=CH), 8.634 (s, 1H, N=CH), 7.292-6.849 (m, 11H, aromatic H), 6.849-6.835 (m, 1H, aromatic H), 4.169 (s, 4H, NCH ₂CH ₂N), 2.510 (m, 18H, aromatic CH ₃).

Embodiment 84 ruthenium complex 6r's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5r (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6r, productive rate: 8% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6r) ¹HNMR (400MHz, CDCl ₃): δ 19.25 (d, J=10.8Hz, Ru=CH), 8.856 (d, J=9.2Hz, 1H, N=CH), 7.894 (m, 3H, aromatic H), 7.521-7.428 (m, 5H, aromatic H), 2.508-1.742 (m, 33H, PCy ₃).

Embodiment 85 ruthenium complex 6s' is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5s (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6s, productive rate: 37% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6s) ¹HNMR (400MHz, CDCl ₃): δ 16.52 (s, 1H, Ru=CH), 8.43 (s, 1H, N=CH), 8.10 (s, 1H, aromatic H), 7.46-7.22 (m, 2H, aromatic H), 7.73-6.96 (m, 8H, aromatic H), 4.19 (s, 4H, NCH ₂CH ₂N), 3.947 (s, 3H, OCH ₃), 3.87 (s, 3H, OCH ₃), 2.49 (s, 12H, aromatic CH ₃), 2.48 (s, 6H, aromatic CH ₃).

Embodiment 86 ruthenium complex 6t's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5t (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow-green colour solid product 6t, productive rate with methyl alcohol or pentane-DCM washing then:--%.

After testing, ruthenium complex (6t) ¹HNMR (400MHz, CDCl ₃): δ 17.43 (d, J=4.8Hz, Ru=CH), 8.56 (s, 1H, N=CH), 8.32-8.10 (m, 2H, aromatic H), 7.28-6.96 (m, 5H, aromatic H), 4.40 (s, 3H, OCH ₃), 3.86 (s, 3H, OCH ₃), 2.33-1.30 (m, 33H, PCy ₃).

Embodiment 87 ruthenium complex 6u's is synthetic:

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5u (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains gray solid product 6u, productive rate: 17% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6u) ¹HNMR (400MHz, CDCl ₃): δ 17.40 (d, J=11.1Hz, Ru=CH), 8.519 (m, 1H, N=CH), 8.333-8.190 (m, 4H, aromatic H), 7.405-7.175 (m, 3H, aromatic H), 4.39 (s, 3H, OCH ₃), 2.31-0.82 (m, 33H, PCy ₃).

Embodiment 88 ruthenium complex 6v's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5v (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains red solid product 6v, productive rate: 28% with methyl alcohol or pentane-DCM washing then.Product is not very stable, is difficult to purification assays ruthenium complex 6v's ¹The H-NMR structure, but its impure ruthenium complex 6v can be directly used in olefin metathesis metathesis catalyzed reaction.

Embodiment 89 ruthenium complex 6w's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5w (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 6w, productive rate: 22% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6w) ¹H-NMR (400MHz, CDCl ₃): δ 18.659 (s, 1H, Ru=CH), 8.556 (s, 1H, N=CH), 7.499-7.337 (m, 2H, aromatic H), 7.256 (s, 4H, aromatic H), 7.004-6.397 (m, 5H, aromatic H), 4.138 (s, 4H, NCH ₂CH ₂N), 3.805 (s, 3H, OCH ₃), 2.493 (m, 18H, aromatic CH ₃).

Embodiment 90 ruthenium complex 6y's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5y (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 6y, productive rate: 9% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6y) ¹H-NMR (400MHz, CDCl ₃): δ 18.96 (s, 1H, Ru=CH), 8.43 (s, 1H, N=CH), 7.42-6.94 (m, 9H, aromatic H), 6.39 (d, J=9.2Hz, 1H, aromatic H), 4.01 (s, 4H, NCH ₂CH ₂N), 2.67-2.28 (m, 20H, aromatic CH, aromatic CH ₃), 0.92 (d, J=7.6Hz, OCH (CH ₃) ₂), 0.83 (d, J=7.6Hz, OCH (CH ₃) ₂).

Embodiment 91 ruthenium complex 6z's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 5z (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 6z, productive rate: 9% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (6z) ¹H-NMR (400MHz, CDCl ₃): δ 18.60 (s, 1H, Ru=CH), 9.88 (s, 1H, N=CH), 7.79-6.96 (m, 8H, aromatic H), 6.54 (d, J=9.2Hz, 1H, aromatic H), 4.18 (s, 4H, NCH ₂CH ₂N), 2.48-2.31 (m, 27H, aromatic CH ₃).

Below be to adopt the synthetic ruthenium complex 8a-8t of complex compound part (7a-7t) according to pertinent data:

Below be the structural formula (1a:Cy=cyclohexyl, 1b:Mes=2,4,6-Three methyl Benzene) of complex compound 8a-8t:

Embodiment 92 ruthenium complex 8a's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7a (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8a, productive rate: 32% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8a) ¹HNMR (400MHz, CDCl ₃): δ 16.80 (s, 1H, Ru=CH), 7.07 (s, 4H, aromatic H), 6.94 (m, 1H, aromatic H), 6.30 (d, J=6.4Hz, 1H, aromatic H), 4.11 (s, 4H, NCH ₂CH ₂N), 2.69 (s, 6H, NCH ₃), 2.49 (s, (s, 12H, aromatic CH ₃), 2.42 (s, 6H, aromatic CH ₃).

Embodiment 93 ruthenium complex 8b's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7b (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8b, productive rate: 79% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8b) ¹HNMR (400MHz, CDCl ₃): δ 16.695 (s, 1H, Ru=CH), 7.368 (m, 1H, aromatic H), 7.037-6.91 (m, 6H, aromatic H), 6.717 (d, J=7.6Hz, 1H, aromatic H), 5.050 (d, J=11.6Hz, 1H, NCH ₂), 3.876-3.846 (m, 4H, NCH ₂CH ₂N), 3.519 (s, 3H, OCH ₃), 3.438 (d, J=11.6Hz, 1H, NCH ₂), 2.85-1.50 (m, 21H, NCH ₃, aromatic CH ₃).

Embodiment 94 ruthenium complex 8c's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7c (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8c, productive rate: 9% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8c) ¹HNMR (400MHz, CDCl ₃): δ 16.967 (s, 1H, Ru=CH), 8.400 (dd, J=8.8,2.4Hz, 1H, aromatic H), (7.65 d, J=2.4Hz, 1H, aromatic H), 7.29 (d, J=8.8Hz, 1H, aromatic H), 7.07 (s, 4H, aromatic H), 4.199 (s, 4H, NCH ₂CH ₂N), 2.567 (s, 6H, N (CH ₃) ₂, 2.473 (s, 12H, aromatic CH ₃), 2.390 (s, 6H, aromatic CH ₃).

Embodiment 95 ruthenium complex 8d's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7d (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8d, productive rate: 24% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8d) ¹HNMR (400MHz, CDCl ₃): δ 16.691 (s, 1H, Ru=CH), 8.356 (dd, J=8.8,2.4Hz, 1H, aromatic H), 7.618 (d, J=2.4Hz, 1H, aromatic H), 7.180 (d, J=8.8Hz, 1H, aromatic H), 7.167-6.999 (m, 4H, aromaticH), 4.164-3.795 (m, 6H, aromatic H), 2.838-2.076 (m, 21H, NCH ₃, aromaticCH ₃), 0.574 (t, J=6.8Hz, 3H, CH ₂CH ₃).

Embodiment 96 ruthenium complex 8e's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7e (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8e, productive rate: 74% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8e) ¹HNMR (400MHz, CDCl ₃): δ 16.559 (s, 1H, Ru=CH), 8.331 (dd, J=8.4,2.4Hz, 1H, aromatic H), 7.563 (d, J=2.4Hz, 1H, aromatic H), 7.197-6.939 (m, 5H, aromatic H), 5.215 (d, J=11.2Hz, 1H, NCH ₂), 4.210-3.959 (m, 4H, NCH ₂CH ₂N), 3.559 (s, 3H, OCH ₃), 3.535 (d, J=11.2Hz, 1H, NCH ₂), 2.938-0.923 (m, 21H, NCH ₃, aromatic CH ₃).

Embodiment 97 ruthenium complex 8f's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7f (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8f, productive rate: 8% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8f) ¹HNMR (400MHz, CDCl ₃): δ 16.820 (s, 1H, Ru=CH), 7.171-7.007 (m, 7H, aromatic H), 6.773 (d, J=2Hz, 1H, aromatic H), 6.602 (d, J=2.8Hz, 1H, aromatic H), (6.550 d, J=8.4Hz, 1H, aromatic H), 4.116 (s, 4H, NCH ₂CH ₂N), 3.262 (s, 3H, OCH ₃), 2.734 (s, 3H, NCH ₃), 2.572-2.260 (m, 18H, aromatic CH ₃).

Embodiment 98 ruthenium complex 8g's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7g (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8g, productive rate: 9% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8g) ¹H-NMR (400MHz, CDCl ₃): δ 17.661 (m, 1H, Ru=CH), 7.573 (d, J=2Hz, 1H, aromatic H), 7.477 (d, J=3Hz, 1H, aromaticH), 7.433 (dd, J=2,8.4Hz, 1H, aromatic H), 7.270 (d, J=3Hz, 1H, aromaticH), (6.983 d, J=8.4Hz, 1H, aromatic H), 4.626 (d, J=13.2Hz, 1H, NCH ₂), 3.978 (d, J=13.2Hz, 1H, NCH ₂), 3.646 (s, 3H, OCH ₃), 2.836 (s, 3H, NCH ₃), 2.412-0.837 (m, 33H, PCy ₃).

Embodiment 99 ruthenium complex 8h's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7h (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8h, productive rate: 37% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8h) ¹H-NMR (400MHz, CDCl ₃): δ 16.843 (s, 1H, Ru=CH), 7.184 (d, J=8.4Hz, 1H, aromatic H), 7.807 (m, 5H, aromatic H), (6.748 m, 1H, aromatic H), 6.619 (d, J=8.8Hz, 1H, aromatic H), 6.320 (d, J=8.4Hz, 1H, aromatic H), 4.294-4.238 (m, 1H, OCH), 4.109 (s, 4H, NCH ₂CH ₂N), 3.846 (d, J=14.0Hz, 1H, NCH ₂), 3.094 (d, J=14.0Hz, 1H, NCH ₂), 2.737 (s, 3H, NCH ₃), 2.429-2.278 (m, 18H, aromatic CH ₃), 1.095 (d, J=6Hz, 6H, OCH (CH ₃) ₂).

Embodiment 100 ruthenium complex 8j's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7h (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8j, productive rate: 48% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8j) ¹H-NMR (400MHz, CDCl ₃): δ 17.584 (d, J=6.0Hz, 1H, Ru=CH), 7.585-7.549 (m, 2H, aromatic H), 7.478 (d, J=8.4Hz, 1H, aromatic H), 7.223 (dd, J=2.4,8.8Hz, 1H, aromatic H), 7.137 (d, J=8.4Hz, 1H, aromatic H), (6.784 d, J=8.8Hz, 1H, aromatic H), 4.802 (d, J=12.8Hz, 1H, NCH ₂), 4.500-4.470 (m, 1H, OCH), 4.049 (d, J=12.8Hz, 1H, NCH ₂), 2.704 (s, 3H, NCH ₃), 2.384-0.780 (m, 39H, PCy ₃, OCH (CH ₃) ₂).

Embodiment 101 ruthenium complex 8k's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7k (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8k, productive rate: 77% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8k) ¹H-NMR (400MHz, CDCl ₃): δ 16.872 (s, 1H, Ru=CH), 7.409 (dd, J=2,8.4Hz, 1H, aromatic H), 7.187-7.132 (m, 5H, aromatic H), 7.031 (d, J=8.4Hz, 1H, aromatic H), (6.925 d, J=7.2Hz, 1H, aromatic H), 6.772-6.757 (m, 2H, aromatic H), 6.652 (t, J=7.2Hz, 1H, aromaticH), 4.655 (d, J=12.4Hz, 1H, NCH ₂), 4.477-4.432 (m, 1H, OCH), 4.015-3.983 (m, 5H, NCH ₂CH ₂N, NCH ₂), 2.535-2.304 (m, 18H, aromatic CH ₃), 2.246 (s, 3H, NCH ₃), 1.285 (d, J=6Hz, 6H, OCH (CH ₃) ₂).

Embodiment 102 ruthenium complex 8m's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7m (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8m, productive rate: 23% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8m) ¹H-NMR (400MHz, CDCl ₃): δ 17.718 (m, 1H, Ru=CH), 7.846 (d, J=6.4Hz, 1H, aromatic H), 7.572 (d, J=2Hz, 1H, aromaticH), 7.528 (dd, J=2.4,8.4Hz, 1H, aromatic H), 7.333-7.233 (m, 2H, aromatic H), 6.980-6.890 (m, 2H, aromatic H), 4.939 (d, J=12.4Hz, 1H, NCH ₂), 4.588-4.543 (m, 1H, OCH), 4.245-4.207 (m, 1H, NCH ₂), 2.639 (s, 3H, NCH ₃), 2.418-0.810 (m, 39H, PCy ₃, OCH (CH ₃) ₂).

Embodiment 103 ruthenium complex 8q's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7q (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8q, productive rate: 59% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8g) ¹H-NMR (400MHz, CDCl ₃): δ 16.80 (s, 1H, Ru=CH), 8.18 (dd, J=8.8,2.4Hz, 1H, aromatic H), (7.46 d, J=2.4Hz, 1H, aromatic H), 7.23 (d, J=8.8Hz, 1H, aromatic H), 7.07 (s, 4H, aromatic H), 4.11 (s, 4H, NCH ₂CH ₂N), 3.91 (s, 3H, COOCH ₃), 2.58 (s, 6H, N (CH ₃) ₂, 2.47 (s, 12H, aromatic CH ₃), 2.43 (s, 6H, aromatic CH ₃).

Embodiment 104 ruthenium complex 8s' is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7s (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8s, productive rate: 43% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8s) ¹H-NMR (400MHz, CDCl ₃): δ 16.64 (s, 1H, Ru=CH), 8.34 (dd, J=8.4,2.4Hz, 1H, aromatic H), 7.54 (d, J=2.4Hz, 1H, aromatic H), 7.25-6.93 (m, 5H, aromatic H), 5.17 (d, J=11.2Hz, 1H, NCH ₂), 4.84-4.83 (m, 1H, OCH), 4.14-3.93 (m, 4H, NCH ₂CH ₂N), 3.45 (d, J=11.2Hz, 1H, NCH ₂), 2.89-1.19 (m, 27H, NCH ₃, aromatic CH ₃, OCH (CH ₃) ₂).

Embodiment 105 ruthenium complex 8t's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 7t (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 8t, productive rate: 87% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (8t) ¹H-NMR (400MHz, CDCl ₃): δ 16.82 (s, 1H, Ru=CH), 7.12-7.02 (m, 5H, aromatic H), 6.64 (m, 1H, aromatic H), 6.51-6.48 (m, 1H, aromatic H), 4.15 (s, 4H, NCH ₂CH ₂N), 3.95-3.92 (m, 1H, NH, NCH ₂), 3.74 (s, 3H, OCH ₃), 2.50-2.37 (m, 18H, aromatic CH ₃), 0.96 (d, J=6.4Hz, 1H, CH ₃).

Below be to adopt the synthetic ruthenium complex 10a-10j of complex compound part (9a-9j) according to pertinent data:

Below be the structural formula (1a:Cy=cyclohexyl, 1b:Mes=2,4,6-Three methyl Benzene) of complex compound 10a-10j:

Embodiment 106 ruthenium complex 10a's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 9a (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 10a, productive rate: 19% with methyl alcohol or pentane-DCM washing then.Product is not very stable, is difficult to purification assays ruthenium complex 10a's ¹The HNMR structure, but its impure ruthenium complex 10a can be directly used in olefin metathesis metathesis catalyzed reaction.

Embodiment 107 ruthenium complex 10b's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 9b (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1a (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 10b, productive rate: 15% with methyl alcohol or pentane-DCM washing then.Product is not very stable, is difficult to purification assays ruthenium complex 10b's ¹The HNMR structure, but its impure ruthenium complex 10b can be directly used in olefin metathesis metathesis catalyzed reaction.

Embodiment 108 ruthenium complex 10c's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 9c (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains reddish-brown solid phase prod 10c, productive rate: 4% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (10c) ¹HNMR (400MHz, CDCl ₃): δ 18.675 (s, 1H, Ru=CH), 8.436 (dd, J=8.4,2.4Hz, 1H, aromatic H), (8.200 d, J=8.4Hz, 1H, aromatic H), 7.604 (d, J=2.4Hz, 1H, aromatic H), 7.132 (s, 4H, aromatic H), 4.140 (s, 4H, NCH ₂CH ₂N), 3.973 (s, 3H, OCH ₃), 2.481 (s, 12H, aromatic CH ₃), 2.459 (s, 6H, aromatic CH ₃).

Embodiment 109 ruthenium complex 10d's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 9d (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow solid product 10d, productive rate: 34% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (10d) ¹HNMR (400MHz, CDCl ₃): δ 18.71 (s, 1H, Ru=CH), 8.42 (dd, J=9,2.4Hz, 1H, aromatic H), (8.18 d, J=9Hz, 1H, aromatic H), 7.60 (d, J=2.4Hz, 1H, aromatic H), 7.13 (s, 4H, aromatic H), 5.25 (m, 1H, OCH (CH ₃) ₂), 4.13 (s, 4H, NCH ₂CH ₂N), 2.46 (m, 18H, aromatic CH ₃), 1.24 (d, 6H, J=6Hz, CH (CH ₃) ₂).

Embodiment 110 ruthenium complex 10e's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 9e (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 10e, productive rate: 34% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (10e) ¹HNMR (400MHz, CDCl ₃): δ 18.56 (s, 1H, Ru=CH), 7.977 (d, J=8.8Hz, 1H, aromatic H), 8.18 (dd, J=8.8,2.4Hz, 1H, aromatic H), 7.105 (s, 4H, aromatic H), (7.064 d, J=2.4Hz, 1H, aromatic H), 5.226 (m, 1H, OCH (CH ₃) ₂), 4.114 (s, 4H, NCH ₂CH ₂N), 2.451 (m, 18H, aromaticCH ₃), 1.281 (d, 6H, J=6Hz, CH (CH ₃) ₂).

Embodiment 111 ruthenium complex 10f's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 9f (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains yellow solid product 10f, productive rate: 41% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (10f) ¹HNMR (400MHz, CDCl ₃): δ 18.75 (s, 1H, Ru=CH), 8.446 (dd, J=8.8,1.6Hz, 1H, aromatic H), 8.208 (d, J=8.8Hz, 1H, aromatic H), 7.637 (d, J=1.6Hz, 1H, aromatic H), and 7.388-7.250 (m, 2H), 7.168 (s, 4H, aromatic H), 6.828 (d, J=8.8Hz, 1H, aromatic H), 5.370 (s, 2H, OCH ₂), 4.529 (m, 1H, OCH (CH ₃) ₂), 4.151 (s, 4H, NCH ₂CH ₂N), 2.511 (m, 18H, aromaticCH ₃), 1.395 (d, 6H, J=6Hz, CH (CH ₃) ₂).

Embodiment 112 ruthenium complex 10g's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 9g (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 10g, productive rate: 53% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (10g) ¹HNMR (400MHz, CDCl ₃): δ 18.601 (s, 1H, Ru=CH), 8.011 (d, J=8.4Hz, 1H, aromatic H), 7.590 (dd, J=1.6,8.4Hz, 1H, aromatic H), 7.306-7.228 (m, 1H, aromatic H), 7.237 (dd, J=2.8,8.8Hz, 1H, aromatic H), 6.811 (d, J=8.8Hz, 1H, aromatic H), 6.713 (d, J=2.0Hz, 1H, aromatic H), 5.334 (s, 2H, OCH ₂), 4.515 (m, 1H, OCH (CH ₃) ₂), 4.159 (s, 4H, NCH ₂CH ₂N), 2.514 (s, 12H, aromatic CH ₃), 2.482 (s, 6H, aromatic CH ₃), 1.277 (d, 6H, J=6Hz, CH (CH ₃) ₂).

Embodiment 113 ruthenium complex 10h's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 9h (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 10h, productive rate: 23% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (10h) ¹HNMR (400MHz, CDCl ₃): δ 18.603 (s, 1H, Ru=CH), 8.003 (d, J=8.8Hz, 1H, aromatic H), 7.553 (d, J=8.4Hz, 1H, aromatic H), 7.320-7.288 (m, 1H, aromatic H), 7.140 (s, 4H, aromatic H), 7.008-6.703 (m, 4H, aromatic H), 5.378 (s, 2H, OCH ₂), 4.560 (m, 1H, OCH (CH ₃) ₂), 4.158 (s, 4H, NCH ₂CH ₂N), 2.712 (s, 12H, aromatic CH ₃), 2.515 (s, 6H, aromatic CH ₃), 1.315 (d, 6H, J=6Hz, CH (CH ₃) ₂).

Embodiment 114 ruthenium complex 10j's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces part 9j (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 10j, productive rate: 37% with methyl alcohol or pentane-DCM washing then.

After testing, ruthenium complex (10j) ¹H-NMR (400MHz, CDCl ₃): ¹H-NMR (400MHz, CDCl ₃): δ 18.74 (s, 1H, Ru=CH), 8.21 (dd, J=8,2.4Hz, 1H, aromatic H), (8.08 d, J=8Hz, 1H, aromatic H), 7.54 (d, J=2.4Hz, 1H, aromatic H), 7.12 (s, 4H, aromatic H), 5.32 (m, 1H, OCH (CH ₃) ₂), 5.25 (m, 1H, OCH (CH ₃) ₂), 4.13 (s, 4H, NCH ₂CH ₂N), 2.47 (m, 18H, aromatic CH ₃), 1.43 (d, J=6Hz, CH (CH ₃) ₂), 1.24 (d, 6H, J=6Hz, CH (CH ₃) ₂).

Below be to adopt the synthetic ruthenium complex 12a-12j of complex compound part (11a-11j) according to pertinent data:

Below be the structural formula (1a:Cy=cyclohexyl, 1b:Mes=2,4,6-Three methyl Benzene) of complex compound 12a-12j:

Embodiment 115 ruthenium complex 12a's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces ligand 1 1a (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 12a, productive rate: 75% with methyl alcohol or pentane-DCM washing then.Product is not very stable, be difficult to the structure of purification assays ruthenium complex 12a, but its impure ruthenium complex 12a can be directly used in olefin metathesis metathesis catalyzed reaction.

Embodiment 116 ruthenium complex 12b's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces ligand 1 1b (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 12b, productive rate: 57% with methyl alcohol or pentane-DCM washing then.Product is not very stable, be difficult to the structure of purification assays ruthenium complex 12b, but its impure ruthenium complex 12b can be directly used in olefin metathesis metathesis catalyzed reaction.

Embodiment 117 ruthenium complex 12c's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces ligand 1 1c (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 12c, productive rate: 40% with methyl alcohol or pentane-DCM washing then.Product is not very stable, be difficult to the structure of purification assays ruthenium complex 12c, but its impure ruthenium complex 12c can be directly used in olefin metathesis metathesis catalyzed reaction.

Embodiment 118 ruthenium complex 12d's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces ligand 1 1d (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 12d, productive rate: 42% with methyl alcohol or pentane-DCM washing then.Product is not very stable, be difficult to the structure of purification assays ruthenium complex 12d, but its impure ruthenium complex 12d can be directly used in olefin metathesis metathesis catalyzed reaction.

Embodiment 119 ruthenium complex 12e's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces ligand 1 1e (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 12e, productive rate: 69% with methyl alcohol or pentane-DCM washing then.Product is not very stable, be difficult to the structure of purification assays ruthenium complex 12e, but its impure ruthenium complex 12e can be directly used in olefin metathesis metathesis catalyzed reaction.

Embodiment 120 ruthenium complex 12f's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces ligand 1 1f (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 12f, productive rate: 63% with methyl alcohol or pentane-DCM washing then.Product is not very stable, be difficult to the structure of purification assays ruthenium complex 12f, but its impure ruthenium complex 12f can be directly used in olefin metathesis metathesis catalyzed reaction.

Embodiment 121 ruthenium complex 12g's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces ligand 1 1g (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 12g, productive rate: 69% with methyl alcohol or pentane-DCM washing then.Product is not very stable, be difficult to the structure of purification assays ruthenium complex 12g, but its impure ruthenium complex 12g can be directly used in olefin metathesis metathesis catalyzed reaction.

Embodiment 122 ruthenium complex 12h's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces ligand 1 1h (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 12h, productive rate: 61% with methyl alcohol or pentane-DCM washing then.Product is not very stable, be difficult to the structure of purification assays ruthenium complex 12h, but its impure ruthenium complex 12h can be directly used in olefin metathesis metathesis catalyzed reaction.

Embodiment 123 ruthenium complex 12j's is synthetic

Two mouthfuls of flasks of a 50mL add successively after with argon replaces ligand 1 1j (10mmol), CuCl (30mmol, 3eq) and 30mL exsiccant DCM, again with after the argon replaces three times with argon gas ball protection enclosed system.Argon shield added down ruthenium complex 1b (12mmol), room temperature reaction 0.5 hour.Reaction finishes, and filters to add silica gel system sand in the rear filtrate, obtains thick product through silica gel column chromatography, obtains green solid product 12j, productive rate: 46% with methyl alcohol or pentane-DCM washing then.Product is not very stable, be difficult to the structure of purification assays ruthenium complex 12j, but its impure ruthenium complex 12j can be directly used in olefin metathesis metathesis catalyzed reaction.

Below be to adopt the synthetic ruthenium complex 13a-13ag of ruthenium complex (13-SM) according to pertinent data:

Below be the structural formula (1a:Cy=cyclohexyl, 1b:Mes=2,4,6-Three methyl Benzene) of ruthenium complex 13a-13ag:

Embodiment 124 ruthenium complex 13a's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13a, productive rate: 47% after the filtration.

After testing, ruthenium complex (13a) ¹H-NMR (400MHz, CDCl ₃): δ 17.33 (s, 1H), 8.71 (s, 1H), 8.56 (d, J=3.2Hz, 1H), 7.84 (d, J=6.0Hz, 1H), 7.41-7.34 (m, 1H), 7.23-7.21 (m, 1H), 7.01 (dd, J=3.2,9.6Hz), 5.23-5.21 (m, 1H), 2.37-0.90 (m, 33H).

Embodiment 125 ruthenium complex 13b's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13b, productive rate: 48% after the filtration.

After testing, ruthenium complex (13b) ¹H-NMR (400MHz, CDCl ₃): δ 16.49 (s, 1H), 8.90-8.50 (m, 2H), 7.86 (d, J=7.2Hz, 1H), 7.47 (dd, J=2.0,7.2Hz, 1H), 7.33 (m, 1H), 7.27 (m, 1H), 7.08 (s, 3H), 6.90 (d, J=1.6Hz, 1H), 6.74-6.72 (m, 1H), 4.87-4.84 (m, 1H), 4.19 (s, 4H), 2.48-2.42 (m, 18H), 1.27 (d, J=4.0Hz, 6H).

Embodiment 126 ruthenium complex 13d's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13d, productive rate: 42% after the filtration.

After testing, ruthenium complex (13d) ¹H-NMR (400MHz, CDCl ₃): δ 17.33 (s, 1H), 8.55 (m, 4H), 7.71 (m, 1H), 7.50 (m, 1H), 7.33-7.28 (m, 4H), 7.02 (m, 1H), 5.23 (m, 1H), 2.34-1.30 (m, 33H).

Embodiment 127 ruthenium complex 13e's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13e, productive rate: 95% after the filtration.

After testing, ruthenium complex (13e) ¹H-NMR (400MHz, CDCl ₃): δ 16.56 (s, 1H), 7.47 (dd, J=2.0,7.2Hz, 1H), and 7.31-7.27 (m, 5H), 7.20-7.19 (m, 3H), 7.08-6.94 (m, 1H), 6.72 (d, J=6.4Hz, 1H), and 4.85-4.81 (m, 1H), 4.18 (s, 3H), 3.85 (s, 4H), 2.48-2.31 (m, 18H), 1.26 (d, J=6.0Hz, 6H).

Embodiment 128 ruthenium complex 13g's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13g, productive rate: 52% after the filtration.

After testing, ruthenium complex (13g) ¹H-NMR (400MHz, CDCl ₃): δ 16.49 (s, 1H), 8.67 (m, 2H), 7.47 (d, J=5.6Hz, 1H), 7.37 (m, 3H), 7.08 (s, 3H), 6.73 (d, J=6.8Hz, 1H), 4.85-4.83 (m, 1H), 4.19 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J=4.4Hz, 6H).

Embodiment 129 ruthenium complex 13h's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13h, productive rate: 59% after the filtration.

After testing, ruthenium complex (13h) ¹H-NMR (400MHz, CDCl ₃): δ 16.52 (s, 1H), 8.60-8.51 (m, 2H), 7.67 (d, J=8.0Hz, 2H), 7.46 (d, J=2.4Hz, 1H), 7.06 (s, 4H), 6.88 (d, J=2.4Hz, 1H), 6.71 (d, J=8.0Hz, 2H), 4.84-4.81 (m, 1H), 4.16 (s, 4H), 2.45-2.39 (m, 18H), 1.24 (d, J=4.0Hz, 6H).

Embodiment 130 ruthenium complex 13j's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13j, productive rate: 81% after the filtration.

After testing, ruthenium complex (13j) ¹H-NMR (400MHz, CDCl ₃): δ 16.56 (s, 1H), 7.90 (d, J=3.2Hz, 2H), 7.83-7.30 (m, 9H), 7.21 (s, 4H), 6.72 (d, J=7.6Hz, 1H), 4.84-4.82 (m, 1H), 4.19 (s, 4H), 2.48-2.31 (m, 18H), 1.26 (d, J=4.8Hz, 6H).

Embodiment 131 ruthenium complex 13k's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13k, productive rate: 36% after the filtration.

After testing, ruthenium complex (13k) ¹H-NMR (400MHz, CDCl ₃): δ 17.39 (s, 1H), 8.89 (s, 2H), 8.63 (d, J=3.2Hz, 2H), 7.86-6.98 (m, 6H), 6.99 (d, J=4.0Hz, 2H), 5.19 (m, 1H), 2.37-0.89 (m, 39H).

Embodiment 132 ruthenium complex 13m's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13m, productive rate: 35% after the filtration.

After testing, ruthenium complex (13m) ¹H-NMR (400MHz, CDCl ₃): δ 17.39 (s, 1H), 8.83 (d, J=15.6Hz, 2H), 8.61 (s, 2H), 7.86-7.38 (m, 6H), 7.00 (m, 1H), 5.20 (m, 1H), 2.37-0.89 (m, 39H).

Embodiment 133 ruthenium complex 13n's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13n, productive rate: 49% after the filtration.

After testing, ruthenium complex (13n) ¹H-NMR (400MHz, CDCl ₃): δ 16.56 (s, 1H), 8.75 (d, J=3.2Hz, 2H), 8.07-7.47 (m, 8H), 7.21 (s, 4H), 6.72 (d, J=7.6Hz, 1H), 4.84-4.82 (m, 1H), 4.19 (s, 4H), 2.69-2.31 (m, 18H), 1.24 (d, J=4.8Hz, 6H).

Embodiment 134 ruthenium complex 13p's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13p, productive rate: 52% after the filtration.

After testing, ruthenium complex (13p) ¹H-NMR (400MHz, CDCl ₃): δ 17.39 (s, 1H), 8.85 (s, 2H), 8.57 (d, J=3.2Hz, 2H), 7.85-7.02 (m, 7H), 5.20 (m, 1H), 3.88 (s, 3H), 2.37-0.89 (m, 39H).

Embodiment 135 ruthenium complex 13q's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13q, productive rate: 81% after the filtration.

After testing, ruthenium complex (13q) ¹H-NMR (400MHz, CDCl ₃): δ 16.56 (s, 1H), 7.53 (d, J=3.2Hz, 2H), 7.54-7.38 (m, 5H), 7.04-6.72 (m, 8H), 4.84-4.82 (m, 1H), 4.19 (s, 3H), 3.80 (s, 4H), 2.69-2.31 (m, 18H), 1.26 (d, J=4.8Hz, 6H).

Embodiment 136 ruthenium complex 13r's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13r, productive rate: 37% after the filtration.

After testing, ruthenium complex (13r) ¹H-NMR (400MHz, CDCl ₃): δ 18.67 (s, 1H), 8.40 (m, 1H), 7.47-6.91 (m, 13H), 6.58 (m, 1H), 4.12 (m, 6H), 2.63-2.27 (m, 19H), 1.00 (d, J=4.0Hz, 6H).

Embodiment 137 ruthenium complex 13s' is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13s, productive rate: 73% after the filtration.

After testing, ¹H-NMR (400MHz, CDCl ₃): δ 18.67 (s, 1H), 8.43 (s, 1H), 7.45-7.35 (m, 3H), 7.19-6.93 (m, 10H), 6.60 (d, J=7.6Hz, 1H), 4.15 (m, 6H), 2.52-2.28 (m, 19H), 1.08-0.89 (m, 6H).

Embodiment 138 ruthenium complex 13t's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13t, productive rate: 55% after the filtration.

After testing, ruthenium complex (13t) ¹H-NMR (400MHz, CDCl ₃): δ 18.69 (s, 1H), 8.42 (s, 2H), 7.44-6.93 (m, 15H), 6.60 (dd, J=2.0,7.6Hz, 2H), 4.14 (s, 6H), 2.52-2.27 (m, 18H), 0.98 (d, J=4.4Hz, 6H).

Embodiment 139 ruthenium complex 13u's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13u, productive rate: 63% after the filtration.

After testing, ruthenium complex (13u) ¹H-NMR (400MHz, CDCl ₃): δ 18.69 (s, 1H), 8.42 (s, 2H), 7.62-6.93 (m, 16H), 6.60 (dd, J=2.0,7.6Hz, 2H), 4.14 (s, 6H), 2.52-2.27 (m, 18H), 0.98 (d, J=4.4Hz, 6H).

Embodiment 140 ruthenium complex 13v's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13v, productive rate: 90% after the filtration.

After testing, ¹H-NMR (400MHz, CDCl ₃): δ 18.69 (s, 1H), 8.42 (s, 2H), 7.86-6.93 (m, 15H), 6.60 (dd, J=2.0,7.6Hz, 2H), 4.14 (s, 6H), 3.87 (s, 3H), 2.52-2.27 (m, 18H), 0.98 (d, J=4.4Hz, 6H).

Embodiment 141 ruthenium complex 13w's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13w, productive rate: 49% after the filtration.

After testing, ruthenium complex (13w) ¹H-NMR (400MHz, CDCl ₃): δ 18.67 (s, 1H), 8.40 (m, 1H), 7.69-6.90 (m, 13H), 6.60 (m, 1H), 4.12 (m, 6H), 2.62-2.17 (m, 19H), 1.00 (d, J=4.0Hz, 6H).

Embodiment 142 ruthenium complex 13x's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13x, productive rate: 97% after the filtration.

After testing, ruthenium complex (13x) ¹H-NMR (400MHz, CDCl ₃): δ 16.57 (s, 1H), 7.63-6.69 (m, 11H), 4.83-4.81 (m, 1H), 4.16 (s, 4H), 2.45-2.39 (m, 21H), 1.24 (d, J=4.0Hz, 6H).

Embodiment 143 ruthenium complex 13y's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13y, productive rate: 81% after the filtration.

After testing, ruthenium complex (13y) ¹H-NMR (400MHz, CDCl ₃): δ 16.85 (s, 1H), 8.40-6.83 (m, 15H), 4.95 (m, 1H), 4.16 (s, 3H), 3.80 (s, 4H), 2.46-2.23 (m, 18H), 1.29 (d, J=4.4Hz, 6H).

Embodiment 144 ruthenium complex 13z's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13z, productive rate: 78% after the filtration.

After testing, ruthenium complex (13z) ¹H-NMR (400MHz, CDCl ₃): δ 16.85 (s, 1H), 8.42-7.07 (m, 15H), 4.95 (m, 1H), 4.19 (s, 4H), 2.45-2.29 (m, 18H), 1.29 (d, J=4.4Hz, 6H).

Embodiment 145 ruthenium complex 13aa's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13aa, productive rate: 85% after the filtration.

After testing, ruthenium complex (13aa) ¹H-NMR (400MHz, CDCl ₃): δ 16.85 (s, 1H), 8.47-6.85 (m, 16H), 4.94 (m, 1H), 4.19 (s, 4H), 2.40-2.29 (m, 18H), 1.29 (d, J=4.4Hz, 6H).

Embodiment 146 ruthenium complex 13ab's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13ab, productive rate: 96% after the filtration.

After testing, ruthenium complex (13ab) ¹H-NMR (400MHz, CDCl ₃): δ 17.00 (s, 1H), 8.47-6.82 (m, 11H), 4.90 (m, 1H), 4.17 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J=4.4Hz, 6H).

Embodiment 147 ruthenium complex 13ac's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13ac, productive rate: 95% after the filtration.

After testing, ruthenium complex (13ac) ¹H-NMR (400MHz, CDCl ₃): δ 17.00 (s, 1H), 8.47-6.83 (m, 11H), 4.91 (m, 1H), 4.17 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J=4.4Hz, 6H).

Embodiment 148 ruthenium complex 13ad's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13ad, productive rate: 33% after the filtration.

After testing, ruthenium complex (13ad) ¹H-NMR (400MHz, CDCl ₃): δ 18.65 (s, 1H), 8.56 (s, 1H), 7.84-6.40 (m, 15H), 4.22 (s, 4H), 3.80 (s, 3H), 2.49-2.29 (m, 18H).

Embodiment 149 ruthenium complex 13ae's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13ae, productive rate: 68% after the filtration.

After testing, ruthenium complex (13ae) ¹H-NMR (400MHz, CDCl ₃): δ 18.65 (s, 1H), 8.53 (s, 1H), 7.84-6.00 (m, 19H), 4.14 (s, 4H), 3.86 (s, 3H), 3.80 (s, 3H), 2.49-2.29 (m, 18H).

Embodiment 150 ruthenium complex 13af's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13af, productive rate: 59% after the filtration.

After testing, ruthenium complex (13af) ¹H-NMR (400MHz, CDCl ₃): δ 18.65 (s, 1H), 8.56 (s, 1H), 7.51-6.39 (m, 19H), 4.14 (s, 4H), 3.80 (s, 3H), 2.42-2.29 (m, 18H).

Embodiment 151 ruthenium complex 13ag's is synthetic

Two mouthfuls of flasks of a 25mL add ruthenium complex (0.1g) after with argon replaces, with after the argon replaces three times with argon gas ball protection enclosed system, add the pyridine (1mL) that replaces again room temperature reaction 0.5 hour.Reaction finishes, and adds Skellysolve A (10 ℃ 20mL), obtain yellow-green colour solid phase prod 13ag, productive rate: 69% after the filtration.

After testing, ruthenium complex (13ag) ¹H-NMR (400MHz, CDCl ₃): δ 18.65 (s, 1H), 8.56 (s, 1H), 7.50-6.39 (m, 20H), 4.14 (s, 4H), 3.80 (s, 3H), 2.42-2.29 (m, 18H).

For fully optimizing the synthetic method of all kinds of ruthenium catalysts effectively, reduce cost and resource consumption, the present invention has adopted different synthetic routes to a few class ruthenium catalysts.Under the effect of raw material 4-SM, generate the Cabbeen intermediate, direct again and RuCl at sodium ethylate ₂(PPh ₃) ₃Reaction generates unsettled ruthenium complex intermediate 4-1; The triphenyl phosphorus part of intermediate 4-1 can be by another part PCy ₃(4-2) generate stable ruthenium complex 4bf.Ruthenium complex intermediate 4-1 or 4bf and part H ₂The ruthenium catalyst 4be that the direct substitution generation of IMes (4-3) is more stable and catalytic activity is higher.Ruthenium complex 4be and the direct complexing of part 4-chloropyridine (4-4) reaction generate 13s:

Below be the easy synthetic route of ruthenium complex intermediate 4-1, ruthenium catalyst 4be, 4bf and 13s:

Embodiment 152 ruthenium complex 4bf's is synthetic

A 500mL there-necked flask adds part raw material 4-SM after with argon replaces successively, and (33g, 100mmol 1.0eq.) are dissolved in the 300mL ethanol, stir to add NaOEt down rapidly (400mmol 4.0eq.), is heated to 60 ℃ of reaction half an hour.Add 120mL water after 30 minutes again, with pentane extraction (200mL * 3).Combining extraction liquid, with saturated sodium carbonate solution washing (150mL * 2), saturated common salt water washing (150mL * 2) is concentrated into about 50mL at 0 ℃ behind the anhydrous sodium sulfate drying.Productive rate calculates next step reaction by 50% and feeds intake.

With RuCl ₂(PPh ₃) ₃(29g 20mmol) is dissolved in the 250mL methylene dichloride, is cooled to-78 ℃, add again-70 ℃ above-mentioned diazonium pentane solution (～60mL).After 5 minutes, temperature of reaction slowly rises to room temperature, and adding CuCl (14.7g, 100mmol).After 15 minutes, filter.After filtrate concentrated, column chromatography purification was with gradient elution agent (2:1 normal hexane/methylene dichloride is to absolute dichloromethane).With the product partial concentration, the normal hexane washing, vacuum-drying obtains the unsettled ruthenium complex intermediate of 12.3g 4-1.

Intermediate 4-1 (15.0mmol) is dissolved in the methylene dichloride (30mL), adds three hexamethylene phosphorus (PCy again ₃, 30mmol 2.0eq.), after 20 ℃ of reaction half an hour, with obtaining the deep green solid behind the chromatography column separation and purification product, obtains green solid product 4bf after washing drying with methyl alcohol and normal hexane, slightly productive rate: 53%.Product 4bf is not very stable, is difficult to purification assays ruthenium complex 4bf's ¹The H-NMR structure, but its impure ruthenium complex 4bf can be directly used in preparation 4be or olefin metathesis metathesis catalyzed reaction.

Embodiment 153 ruthenium complex 4be's is synthetic

Two mouthfuls of flasks of a 50mL add ruthenium complex 4bf (5.0mmol) and H after with argon replaces successively ₂IMes (H) (CCl ₃) (4-3; 10.0mmol; 2.0eq.) be dissolved in the 30mL exsiccant and be dissolved in the toluene; again with after the argon replaces three times with argon gas ball protection enclosed system; be heated to 80 ℃, reaction in 1.5 hours finishes the postcooling crystallization filters, and filters in the rear filtrate and obtains deep green solids crude product behind the adding silica gel column chromatography; obtain stable green solid product 4be, productive rate: 59% with methyl alcohol or pentane-DCM washing then.

The preparation of ruthenium complex 13s is formed by the direct complexing of above-mentioned ruthenium complex 4be and part 4-chloropyridine (4-4) reaction, and relevant preparation experiment and analytical results see synthesizing of embodiment 137 described ruthenium complex 13s for details.

The Application Example of ruthenium complex catalyst in olefin metathesis metathesis cyclization:

Below for the inventor at the structural formula of representational complex compound 14a, the 14b in another patent of delivering (US20070043180A1) and other four representational catalyzer 14c, 14d, 14e, 14f before the present invention:

Some ruthenium complex catalysts among these ruthenium catalysts (14a-14f) and the present invention are used for the test of the catalytic cyclization reaction and the high molecular polymer novel material that ring-opening polymerization prepares difference in functionality of following cycloolefin selectively, and the contrast of the catalytic effect of the roughly the same catalyzer of listing with the present invention is discussed.

Ruthenium complex catalysed olefin metathesis reaction experimental procedure: the substrate of 50mg is placed two mouthfuls of round-bottomed flasks of 25mL, with adding new methylene dichloride that steams of 1mL and the catalyzer of 5mg after the argon replaces 5 times.Under argon shield, reaction mixture at room temperature is stirred to and reacts completely.The transformation efficiency of reaction is obtained by the HPLC monitoring.Below be the catalytic activity research of ruthenium complex in the transposition replacement(metathesis)reaction of different alkene:

Effect embodiment 1:

In order to contrast the catalytic activity of the ruthenium complex that contains different substituents, existing catalytic activity and relative catalytic activity to the different ruthenium complex replacement(metathesis)reactions of embodiment synthetic compares.

Transposition cyclisation reaction experiment in the olefin hydrocarbon molecules: in 25ml two neck bottles, add 50mg reaction substrate 15 respectively, make inside be full of argon gas with the threeway displacement, add the 1.0ml methylene dichloride with syringe, after stirring at room makes dissolving fully, above-mentioned ruthenium complex catalyst (the 4a-4cz that adds 2mol% respectively, 6a-6z, 8a-8t, 10a-10j).Respectively at 10min, 30min, 1.0hr, 3.0hr, 5.0hr, 8.0hr, 15.0hr sampling, follow the tracks of reaction with HPLC and LC-MS.With the transformation efficiency of normalized method calculating product, reaction result sees Table 2.

Olefin metathesis metathesis cyclisation product (16) ¹HNMR (400MHz, CDCl ₃): δ=7.78 (d, 2H, J=8.21Hz), 7.31 (m, 7H), 6.01 (m, 1H), 4.47 (m, 2H), 4.30 (m, 2H), 2.41 (s, 3H). molecular weight (M+H ⁺): the m/z calculated value is 300.1, and test value is 300.2.

The activity assessment of the intramolecular cyclization catalysts 4a-4cz of table 1-1. alkene 15

Have active preferably except more than ten listed among above-mentioned table 1-1 new catalyst among the ruthenium catalyst 4a-4cz, the ruthenium catalyst that all the other are listed active relatively poor, the substituting group electronic effect that this shows Novel Ligands has very remarkable influence to the catalytic activity of the ruthenium complex of its formation.

The activity assessment of the intramolecular cyclization catalysts 6a-6z of table 1-2. alkene 15

Have actively preferably except 6s, 6t listed among the above-mentioned table 1-2 and three new catalysts of 6v among the ruthenium catalyst 6a-6z, catalytic activity obviously is better than similar known catalyzer 14f.Remaining ruthenium catalyst active very poor, the substituting group electronic effect that this shows Novel Ligands has very remarkable influence to the catalytic activity of the ruthenium complex of its formation.

The activity assessment of the intramolecular cyclization catalysts 8a-8t of table 1-3. alkene 15

Have actively preferably except 8c, 8e listed among the above-mentioned table 1-3 and three new catalysts of 8h among the ruthenium catalyst 8a-8t, catalytic activity obviously is better than similar known catalyzer 14d.The ruthenium catalyst that all the other are listed active relatively poor, the substituting group electronic effect that this shows Novel Ligands has very remarkable influence to the catalytic activity of the ruthenium complex of its formation.

The activity assessment of the intramolecular cyclization catalysts 10a-10j of table 1-4. alkene 15

Except 10c, 10d listed among the above-mentioned table 1-4,10e, 10f and five new catalysts of 10g activity is preferably arranged among the ruthenium catalyst 10a-10j, catalytic activity obviously is better than similar known catalyzer 14e.Remaining ruthenium catalyst active relatively poor, the substituting group electronic effect that this shows Novel Ligands has very remarkable influence to the catalytic activity of the ruthenium complex of its formation.

The activity assessment of the intramolecular cyclization catalysts 13a-13ag of table 1-5. alkene 15

Except four listed among above-mentioned table 1-5 new catalysts relatively poor activity is arranged among the ruthenium catalyst 13a-13ag, the cyclisation activity of remaining ruthenium catalyst is very poor, and the substituting group electronic effect that this shows Novel Ligands has very remarkable influence to the catalytic activity of the ruthenium complex of its formation.But wherein some catalyzer 13a-13ag can be effective to the cycloolefin ring-opening polymerization.

Several better active catalyzer arranged except what list in above-mentioned each table in the above-mentioned all kinds of novel ruthenium catalyst, the cyclization of the ruthenium catalyst of all the other preparations (RCM) is active very poor, the result shows not to be had substituent ruthenium complex (14f) and has the catalytic activity of substituent ruthenium complex (as 6g and 6m) very low on the novel complex compound part phenyl ring, can't cause the catalytic cyclization reaction (RCM) of alkene.This shows that the novel substituting group electronic effect that contains oxygen or nitrogen ligating atom part among the present invention has very remarkable influence to the catalytic activity of the ruthenium complex of its formation.Table 1-1,1-2,1-3,1-4,1-5 result show, all kinds of new catalyst 4c of the present invention, 4g, 4t, 4u, 4w, 4x, 4aa, 4ab, 4cf, 6s, 6u, 8c, 8e, 8h, 8k, 10c, 10d, 10e, 10f, 10g are better to the specific activity of alkene 15, the ring closure reaction major part finishes in 1.5-3hr, is the reasonable novel olefin metathesis cyclization catalyzer of catalytic activity in present this field.

Effect embodiment 2:

In order to contrast all kinds of catalytic activitys that contain the ruthenium complex of different substituents, now catalytic activity and the relative catalytic activity that better active ruthenium complex catalyst is arranged in the foregoing description compared.

Olefin hydrocarbon molecules intramolecular cyclization reaction experiment: in 25ml two neck bottles, add 50mg reaction substrate 17 respectively, make inside be full of argon gas with the threeway displacement, add the 1.0ml methylene dichloride with syringe, after stirring at room made dissolving fully, the above-mentioned specific activity that adds 2mol% respectively is ruthenium complex catalyst preferably.Respectively at 10min, 30min, 1.0hr, 3.0hr, 5.0hr, 8.0hr, 15.0hr sampling, follow the tracks of reaction with HPLC and LC-MS.With the transformation efficiency of normalized method calculating product, reaction result sees Table 2.

Olefin metathesis metathesis cyclisation product (12) ¹HNMR (400MHz, CDCl ₃): δ=7.78 (d, 2H, J=8.21Hz), 7.31 (m, 7H), 6.01 (m, 1H), 4.47 (m, 2H), 4.30 (m, 2H), 2.41 (s, 3H). molecular weight (M+H ⁺): the m/z calculated value is 300.1, and test value is 300.2.

The intramolecular cyclization of table 2. alkene 17 reacts all kinds of activity of such catalysts assessments

Table 2 is the result show, all kinds of new catalyst 4c of the present invention, 4t, 4x, 4af, 6s, 8e, 10d are better to the specific activity of alkene 17, the ring closure reaction major part finishes in 1.5-3hr, is the reasonable novel olefin metathesis cyclization catalyzer of catalytic activity in present this field.

Effect embodiment 3:

In order to measure the difference between the different high activated catalysts better, this patent has designed on existing two electrophilic fluoro, the alkene two methyl substituted substrates 19 again, and substrate 19 is imitated the difficult characteristic that transposition metathesis cyclisation takes place makes the activity difference between the catalyzer (11a-j) measure out apparent in viewly.

Transposition cyclisation reaction experiment in the olefin hydrocarbon molecules: in 25ml two neck bottles, add the polysubstituted vinylbenzene ether of 50mg reaction substrate alkene 19 respectively, make inside be full of argon gas with the threeway displacement, add the 1.0ml methylene dichloride with syringe, after stirring at room makes dissolving fully, add the above-mentioned ruthenium complex catalyst (12a-12h) of 3mol% respectively.Respectively at 10min, 30min, 1.0hr, 3.0hr, 5.0hr, 8.0hr, 15.0hr sampling, follow the tracks of reaction with HPLC and LC-MS.With the transformation efficiency of normalized method calculating product, relevant kinetic results is listed in table 3.

Olefin metathesis metathesis cyclisation product (20) ¹HNMR (CDCl ₃: δ=7.26ppm): 7.15 (d, 1H, J=2.74Hz), 6.84 (d, 1H, J=2.34Hz), 6.34 (dt, 1H, J=1.95,9.78Hz), 5.86 (d, 1H, J=9.78Hz), 4.95 (m, 2H).Molecular weight (M+H ⁺): the m/z calculated value is 200.99, and test value is 201.1.

The active assessment of the intramolecular cyclization catalytic reaction of table 3. alkene 19

Table 3 is the result show, new catalyst 12a of the present invention, 12b, 12d, 12e, 12g, 12h are active fine to alkene 19, the ring closure reaction major part finished in 30 minutes, was the best novel olefin metathesis cyclization of the class catalyzer of catalytic activity in present this catalytic cyclization field.

The Application Example of ruthenium complex catalyst in the alkene ring-opening polymerization:

In order further to research and develop the mechanical property of more effective alkene ring-opening polymerization catalyst and high molecular polymer novel material thereof, measure the difference between the different high activated catalysts better, the effect embodiment 4-7 by following alkene ring-opening polymerization researches and develops mechanical propertys such as intensity that contrast improves olefin metathesis reaction catalyzer and high molecular polymer product and modulus.

Effect embodiment 4:

Method one; Alkene ring-opening polymerization experiment (catalyzed polymerization in the solvent): cyclooctene (21) raw material monomer is dissolved in the anhydrous solvent (as ethylene dichloride DCE) of 20 times of amounts (20x), argon filling is caught up with oxygen, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 ℃) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.After reaction is spent the night reaction solution slowly is poured in the ethanol and is precipitated out, alcohol immersion, after the suction filtration oven dry polymer solids product (22), productive rate is 70%-98%.

Method two; Alkene ring-opening polymerization experiment (solvent-free catalyzed polymerization): the feeding argon gas oxygen of rushing in liquid ring octene monomer (21), add the ruthenium catalyst (0.1-5 ‰) that this project etc. filters out again fast, the reacting by heating several minutes afterreaction liquid thick heat release that becomes sticky gradually between the 20-120 degree, last polymerization obtains open loop high molecular polymer solid product (22).

The result shows, new catalyst 8c of the present invention, 8d, 4j, 4m, 4p, 4r, 4c, 8c, 8e are better to the specific activity of cyclooctene (21) polyreaction, catalyzed polymerization product (22) have preferably tensile strength and modulus (＞1.5Gpa), be the reasonable novel olefin metathesis polymerisation catalysts of catalytic activity in this field at present.Open loop high molecular polymer (22) adds the heat energy fusing and is dissolved in the weak polar solvent (as sherwood oil, paraffin wet goods), and further processing can be used for preparing high-intensity explosion-proof lamp or spinning processing high-strength products.

Effect embodiment 5:

Method one; Alkene ring-opening polymerization experiment (catalyzed polymerization in the solvent): norbornylene (23) raw material monomer is dissolved in the anhydrous solvent (as ethylene dichloride DCE) of 20 times of amounts (20x), argon filling is caught up with oxygen, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 ℃) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.After reaction is spent the night reaction solution slowly is poured in the ethanol and is precipitated out, alcohol immersion, after the suction filtration oven dry polynorbornene solid product (24), productive rate is 75%-98%.

Method two; Alkene ring-opening polymerization experiment (solvent-free catalyzed polymerization): the feeding argon gas oxygen of rushing in liquid norbornene monomer (23), add the ruthenium catalyst (0.1-5 ‰) that this project etc. filters out again fast, the thick heat release that becomes sticky gradually of reacting by heating several minutes afterreaction liquid obtains polynorbornene solid product (24) at last between 25-100 ℃.

The result shows, new catalyst 4c of the present invention, 4h, 4j, 4m, 4p, 4r, 8c, 8d, 8e are better to the specific activity of norbornylene (23), catalytic polymerization finishes in 10-60min, polynorbornene product (24) has intensity, hardness and tensile modulus preferably, is the reasonable novel olefin metathesis polymerisation catalysts of catalytic activity in present this field.Open loop high molecular polymer (24) further processing can be used for preparing high-intensity explosion-proof lamp or spinning material.

Effect embodiment 6:

Method one; Alkene ring-opening polymerization experiment (catalyzed polymerization in the solvent): with the luxuriant diene (DCPD of dicyclo, 25) raw material monomer is dissolved in the anhydrous solvent (as ethylene dichloride DCE) of 20 times of amounts (20x), argon filling is caught up with oxygen, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 ℃) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.After reaction is spent the night reaction solution slowly is poured in the ethanol and is precipitated out, alcohol immersion must be gathered the luxuriant diene of dicyclo (Poly-DCPD) solid product (26) after the suction filtration oven dry, and productive rate is 75%-98%.

Method two; Alkene ring-opening polymerization experiment (solvent-free catalyzed polymerization): at the luxuriant diene monomers (DCPD of liquid dicyclo, 25) feed the argon gas oxygen of rushing in, add the ruthenium catalyst (0.1-5 ‰) that this project etc. filters out again fast, the reacting by heating several minutes afterreaction liquid thick heat release that becomes sticky gradually between the 30-120 degree, last polymerization obtains the poly-luxuriant diene of dicyclo (Poly-DCPD) polymeric solid product (26).

Catalytic result shows, new catalyst 4c of the present invention, 4h, 4j, 4m, 4p, 4am, 4be, 4bg, 4bx, 4cg, 8a, 8b, 8c, 8d, 8e, 8h, 8q are better to the polymerization catalyzed activity of alkene DCPD (25), are the novel preferably olefin metathesis polymerisation catalysts of homogeneous catalysis specific activity in this field at present.Polyreaction is carried out preferable at 40-60 ℃, catalytic polymerization finishes in 10-60min under the differential responses condition.Especially use 4c, 4am, 4be, 4cg or and luxuriant two ene products of poly-dicyclo (26) that obtain of new catalyst polyreaction such as 8h have good intensity, hardness and modulus in flexure.

Polymkeric substance (26) The performance test results shows, the Poly-DCPD solid polymer of solvent-free catalyzed polymerization preparation have good hardness (＞80Gpa), modulus in flexure (＞20Gpa) and heat-drawn wire (＞200 ℃), main performance index is better than the luxuriant diene of the same dicyclo of birdsing of the same feather flock together (Poly-DCPD) product of present U.S. Materia company and Japanese Zeon company.Multipolymers such as the antioxidant of interpolation a small amount of (0.1-5%) or linking agent can improve physicalies such as poly-luxuriant two ene products (26) hardness of dicyclo and modulus during catalyzed polymerization, can make the luxuriant diene of poly-dicyclo (26) product of different high strength, high rigidity, low temperature resistant, acid and alkali-resistance from now on by injection moulding complete processing (ROMP-RIM), in industry and life, have purposes widely.

Effect embodiment 7:

Alkene ring-opening polymerization experiment: olefinic monomer (27) raw material is dissolved in the anhydrous solvent (as ethylene dichloride DCE) of 15 times of amounts (15x), argon filling is caught up with oxygen, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 ℃) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.After reaction is spent the night reaction solution slowly is poured in the ethanol and is precipitated out, alcohol immersion, after the suction filtration oven dry white polymer solid product (28), productive rate is 80-98%.Open loop high molecular polymer (28) further processing can be used for preparing high-intensity spinning material.

Effect embodiment 8:

" Linker " is the group of shack olefinic monomer and functional group " G ", includes but not limited to O, S, C ₁-C ₁₅Saturated or undersaturated alkyl, replacement or unsubstituted C ₁-C ₁₅Amido, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₆-C ₁₅Aryloxy, replacement or unsubstituted C ₁-C ₁₅Heterocyclic oxy group, replacement or unsubstituted C ₁-C ₁₅Alkylthio, replacement or unsubstituted C ₆-C ₁₅Arylthio, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, methanoyl, formamido-, replacement or unsubstituted C ₁-C ₁₅Alkyl carbonyloxy, replacement or unsubstituted C ₁-C ₁₅Alkyl formamides base, replacement or unsubstituted C ₆-C ₁₅Aryl methanoyl, replacement or unsubstituted C ₆-C ₁₅The aryl carboxamides base;

" G " is the compound with property or purposes, as the small molecules liquid crystal (29d, 29e, 29f) and the small-molecule drug (29g that can be connected with " Linker ", " G " is medicine " Lipitor ") etc. material, generate after the monomer ring-opening polymerization of connection have specific characteristics can or the prodrug (30g) of purposes high molecule liquid crystal (30d, 30e, 30f) and macromolecule surface appendix.

Following is the structure of high molecular polymer (30) of the catalysis ring-opening polymerization preparation of cycloolefin:

Alkene ring-opening polymerization experiment: olefinic monomer raw material (29) is dissolved in the anhydrous solvent (as ethylene dichloride DCE) of 20 times of amounts (20x), argon filling is caught up with oxygen, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 ℃) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.After reaction is spent the night reaction solution slowly is poured in the ethanol and is precipitated out, alcohol immersion, after the suction filtration oven dry polymer solids product (30), productive rate is 80%-98%.

Relevant better polymerization reaction result summary is listed as follows (table 4):

Table 4 is the result show, the energy polymerization under the novel ruthenium catalyst effect that this project screening goes out of small molecules liquid crystal or medicine monomer generates the prodrug (30g) of have specific characteristics energy or purposes high molecule liquid crystal (30d, 30e, 30f) and macromolecule surface appendix.Active testing is the result show, new catalyst 4a of the present invention, 4c, 4e, 4g, 6e, 6e and 13a are better to the specific activity of olefinic monomer (29a-g), and polyreaction finishes in 5-15hr, and under the catalyzed polymerization condition of optimizing, productive rate is higher than 90%.The polymerization test result shows, among the present invention dissimilar ruthenium catalyst solvent-free with solvent condition is arranged under have tangible different to different monomers polymeric catalytic activity, especially some novel ruthenium catalyst (as 4a, 6e) catalytic activity in cyclization is very low, but in solvent, then have good catalytic activity in the polyreaction, in cyclisation (RCM) and the reaction of ring-opening polymerization (ROMP) two classes, demonstrate good selectivity and catalytic activity thus.

Effect embodiment 9:

Alkene ring-opening polymerization experiment: the olefinic monomer raw material is dissolved in the anhydrous solvent (as ethylene dichloride DCE) of 20 times of amounts (20x), argon filling is caught up with oxygen, add ruthenium catalyst (4a or 6e that this project etc. filters out again fast, 0.1 ‰-5%), react (20-75 ℃) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.After reaction is spent the night reaction solution slowly is poured in the ethanol and is precipitated out, alcohol immersion, after the suction filtration oven dry polymer solids, productive rate is 60%-98%.

Following is the structure of high molecular polymer 32 (VIc) of the catalysis ring-opening polymerization preparation of cycloolefin:

Relevant better polymerization reaction result summary is listed as follows (table 5):

Table 5 is the result show, the small molecule monomer (31a-31s) that contains difference in functionality group can polymerization generate the high molecular polymer that higher-strength and modulus are arranged under the novel ruthenium catalyst effect that this project screening goes out, wherein the modulus and the tensile strength of testing after polymkeric substance 32a, 32b, 32n, the 32q processing film forming is respectively 0.5-3.0Gpa and 20-40MPa, can be used for spinning processing.

Effect embodiment 10:

Alkene ring-opening polymerization experiment: olefinic monomer raw material 33 (VIIa) is dissolved in the anhydrous solvent (as ethylene dichloride DCE) of 20 times of amounts (20x), argon filling is caught up with oxygen, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 ℃) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.After reaction is spent the night reaction solution slowly is poured in the ethanol and is precipitated out, alcohol immersion, after the suction filtration oven dry polymer solids, productive rate is about 60%-98%.

Following is high molecular polymer 34 (VIIc) structure of the catalysis ring-opening polymerization preparation of cycloolefin:

Relevant better polymerization reaction result summary is listed as follows (table 6):

Table 6 is the result show, the small molecule monomer (33a-33s) that contains difference in functionality group can polymerization generate the high molecular polymer (34) that higher-strength and modulus are arranged under the novel ruthenium catalyst effect that this project screening goes out, polymkeric substance 34a wherein, 34b, 34c, 34v, 34w, the modulus and the tensile strength of testing after the 34x processing film forming are respectively 1.0-16Gpa and 30-50MPa, wherein polymkeric substance 34c and 34x (film forming test modulus up to 16Gpa) are more suitable in the spinning processing high-strength products, are the best family macromolecule polymer architectures of modulus in the product that obtains by alkene ring-opening polymerization (ROMP) at present.

Effect embodiment 11:

Alkene ring-opening polymerization experiment: olefinic monomer raw material 35 (VIIb) is dissolved in the anhydrous solvent (as ethylene dichloride DCE) of 20 times of amounts (20x), argon filling is caught up with oxygen, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 ℃) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.After reaction is spent the night reaction solution slowly is poured in the ethanol and is precipitated out, alcohol immersion, after the suction filtration oven dry polymer solids 36 (VIId), productive rate is about 85-98%.

Following is high molecular polymer (VIId) structure of the catalysis ring-opening polymerization preparation of cycloolefin:

Test result shows that modulus and the tensile strength of polymkeric substance 36a-36d are lower, are less than 0.5GPa and 10MPa respectively, and processing characteristics is not as 34c and 34x.

Effect embodiment 12:

Two or more cycloolefin monomers raw materials (as 21,23,25,27,29,31,33 or 35) mixing among the above-mentioned effect embodiment 5-11 is dissolved in the anhydrous solvent (as ethylene dichloride DCE), add the novel ruthenium catalyst reacting by heating that this project screening goes out again, the high-molecular copolymer that can prepare different performance, concrete copolyreaction is as follows:

Alkene ring-opening polymerization experiment: two or more cycloolefin monomers raw materials are dissolved in the anhydrous solvent (as ethylene dichloride DCE) of 20 times of amounts (20x), argon filling is caught up with oxygen, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 ℃) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.After reaction is spent the night reaction solution slowly is poured in the ethanol and is precipitated out, alcohol immersion, after the suction filtration oven dry polymer solids, productive rate is about 65%-98%.

Above-mentioned two or more cycloolefin monomers can prepare different high-molecular copolymer novel materials by copolyreaction under some catalyst actions of this project research and development, the structure of relevant each analog copolymer is as follows:

Test result shows that the modulus and the tensile strength of testing after polymkeric substance 37j and the 37u processing film forming are respectively 2.0-10Gpa and 40-70MPa, can be used for film forming or spinning processing high-strength products.

Above-mentioned effect embodiment 7-11 result shows, structure is that the high molecular polymer (the film forming modulus is up to 16Gpa) of 34c and 34x is the best class ROMP polymer architecture of modulus in the product that obtains by alkene ring-opening polymerization (ROMP) at present.Catalyzer 4a and 6e have activity and selectivity preferably.

Below instrument and the raw material that relates among the embodiment is described as follows:

Ir data is the Fourier TransformAVATAR that adopts Thermo Nicolet company ^TM360E.S.P ^TMInfrared instrument analysis obtains, with cm ^-1For unit represents.

Proton nmr spectra is that the analysis of Varian Mercury Plus 400 (400MHz) nuclear magnetic resonance spectrometer obtains.Chemical shift is that interior mark comes record with tetramethylsilane, is that unit represents (CHCl with ppm ₃: δ=7.26ppm).The data message of record is as follows: chemical shift and split branch and coupling constant (s: singlet; D: doublet; T: triplet; Q: quartet; Br: broad peak; M: multiplet).

Mass-spectrometric data is removed other to be needed, and all adopts Finnigan Finnigan LCQ Advantage LC-MS instrument to analyze, and institute responds and all operates under the anhydrous and oxygen-free condition that dry argon gas is protected.Solid metal-organic compound is stored in the argon shield loft drier.

All column chromatography silica gel (200-300 order) is bought from Haiyang Chemical Plant, Qingdao.

Tetrahydrofuran (THF) and ether are to obtain through distillation, add sodium Metal 99.5 and benzophenone during distillation therein.Methylene dichloride, pentane and hexane are to handle with hydrolith.Cl ₂Ru=CHPh (PCy ₃) (H ₂IMes) according to document preparation (Jason S.Kingsbury, Joseph P.A.Harrity, Peter J.Bonitatebus, Jr., Amir H.Hoveyda ^*, J.Am.Chem.Soc.1999,121,791; American Chemical Society's magazine was rolled up 791 pages in 1999 121).Other all chemical reagent are bought from Shanghai reagent company.

Claims

1, structural formula is the olefin metathesis metal complex part of formula Ia, Ib, Ic:

Wherein, Z is CH ₂Or

M=0 or 1, n=0 or 1;

During n=1, X ¹And Y ¹Be nitrogen, oxygen, sulphur, CH independently ₂, replacement or unsubstituted C ₁-C ₂₀Alkyl, replacement or unsubstituted C ₆-C ₂₀Aryl, replacement or unsubstituted C ₆-C ₂₀Aryloxy, replacement or unsubstituted C ₂-C ₂₀Heterocyclic aryl, carbonyl, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₂₀Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀Aryl, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₁-C ₂₀Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; X ¹The parent that each group of expression connects is Y ¹, Y ¹The parent that each group of expression connects is X ¹

During m=0, Y is nitrogen, oxygen, replacement or unsubstituted C ₁-C ₂₀Alkoxyl group, replacement or unsubstituted C ₆-C ₂₀Aryloxy, replacement or unsubstituted C ₂-C ₂₀Heterocyclic aryl, carbonyl, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₂₀Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀Aryl, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₁-C ₂₀Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; Among the formula Ia, the parent that the group that Y represents connects is X, and among the formula Ib, the parent that the group that Y represents connects is an aromatic ring, and the parent that the group that Y represents among the Ic connects is for connecting R ₃Carbon;

During m=1, X is nitrogen, oxygen, sulphur, CH, CH ₂, carbonyl; Y is nitrogen, oxygen, CH, methylene radical, replacement or unsubstituted C ₁-C ₂₀Alkoxyl group, replacement or unsubstituted C ₆-C ₂₀Aryl, replacement or unsubstituted C ₆-C ₂₀Aryloxy, replacement or unsubstituted C ₂-C ₂₀Heterocyclic aryl, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₂₀The carbonyl of alkoxyl group, imino-, replacement or unsubstituted _C1-C ₂₀Alkyl imido grpup, unsubstituted C ₁-C ₂₀Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀Aryl, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₁-C ₂₀Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; The parent that the group that X represents connects is Y, and the parent that the group that Y represents connects is X; Between " X=Y " singly-bound or two key;

E ¹Be hydrogen, halogen, nitro, itrile group, C ₁-C ₂₀Alkyl, C ₁-C ₂₀Alkoxyl group, C ₁-C ₂₀Alkylthio, C ₁-C ₂₀Silica-based, the C of alkane ₁-C ₂₀Alkyl siloxy, C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted amino, aminoacyl, connection C ₁-C ₂₀The carbonyl of alkylamino, C ₆-C ₂₀Aryl, C ₆-C ₂₀Aryloxy, sulfoxide group, sulfuryl, aldehyde radical, connection C ₁-C ₂₀The carbonyl of alkyl, connection replace or unsubstituted C ₆-C ₂₀The carbonyl of aryl, connection replace or unsubstituted C ₂-C ₂₀The carbonyl of heterocyclic radical, connection C ₁-C ₂₀The carbonyl of alkoxyl group, connection C ₆-C ₂₀The carbonyl of aryloxy, connection C ₂-C ₂₀The carbonyl of heterocyclyloxy base, urea groups, replacement or unsubstituted C ₁-C ₂₀Alkyl urea groups, replacement or unsubstituted C ₆-C ₂₀Aryl-ureido or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical urea groups;

E ²Be hydrogen, halogen, C ₁-C ₂₀Alkyl, C ₁-C ₂₀Alkoxyl group, C ₁-C ₂₀Alkylthio, C ₁-C ₂₀Silica-based, the C of alkane ₁-C ₂₀Alkyl siloxy, aminoacyl, connection C ₁-C ₂₀The carbonyl of alkylamino, connection C ₆-C ₂₀The carbonyl of arylamino, connection C ₂-C ₂₀The carbonyl of heterocyclic radical amino, C ₆-C ₂₀Aryl, C ₆-C ₂₀Aryloxy, C ₂-C ₂₀Heterocyclic aryl, aldehyde radical, connection C ₁-C ₂₀The carbonyl of alkyl, connection C ₆-C ₂₀The carbonyl of aryl, connection C ₂-C ₂₀The carbonyl of heterocyclic radical, connection C ₁-C ₂₀The carbonyl of alkoxyl group, connection C ₆-C ₂₀The carbonyl of aryloxy, connection C ₂-C ₂₀The carbonyl of heterocyclyloxy base or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₂₀Aryl, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical, replacement or unsubstituted C ₁-C ₂₀Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl formyl radical, replacement or unsubstituted C ₆-C ₂₀Aryl formyl radical, replacement or unsubstituted C ₂-C ₂₀Heterocyclic radical formyl radical, replacement or unsubstituted C ₁-C ₂₀Alkyl sulphonyl, replacement or unsubstituted C ₆-C ₂₀Aryl sulfonyl or replacement or unsubstituted C ₂-C ₂₀The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring;

2, metal complex part according to claim 1 is characterized in that: in formula Ia-Ic,

Z is CH ₂Or TsNHN;

M=0 or 1, n=0 or 1;

During n=1, X ¹And Y ¹Be nitrogen, oxygen, sulphur, CH independently ₂, replacement or unsubstituted C ₁-C ₁₅Alkyl, replacement or unsubstituted C ₆-C ₁₅Aryl, replacement or unsubstituted C ₆-C ₁₅Aryloxy, replacement or unsubstituted C ₂-C ₁₅Heterocyclic aryl, carbonyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₁₅Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₁₅Aryl, replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical, replacement or unsubstituted C ₁-C ₁₅Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₁₅Alkyl formyl radical, replacement or unsubstituted C ₆-C ₁₅Aryl formyl radical or replacement or unsubstituted C ₂-C ₁₅The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; X ¹The parent that each group of expression connects is Y ¹, Y ¹The parent that each group of expression connects is X ¹

During m=0, Y is nitrogen, oxygen, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₆-C ₁₅Aryloxy, replacement or unsubstituted C ₂-C ₁₅Heterocyclic aryl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₁₅Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₁₅Aryl, replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical, replacement or unsubstituted C ₁-C ₁₅Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₁₅Alkyl formyl radical, replacement or unsubstituted C ₆-C ₁₅Aryl formyl radical or replacement or unsubstituted C ₂-C ₁₅The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; Among the formula Ia, the parent that the group that Y represents connects is X, and among the formula Ib, the parent that the group that Y represents connects is an aromatic ring, and the parent that the group that Y represents among the Ic connects is for connecting R ₃Carbon;

During m=1, X is nitrogen, oxygen, sulphur, CH, CH ₂, carbonyl; Y is nitrogen, oxygen, CH, methylene radical, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₆-C ₁₅Aryl, replacement or unsubstituted C ₆-C ₁₅Aryloxy, replacement or unsubstituted C ₂-C ₁₅Heterocyclic aryl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, replacement or unsubstituted C ₁-C ₁₅Imido grpup; Suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₁₅Aryl, replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical, replacement or unsubstituted C ₁-C ₁₅Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₁₅Alkyl formyl radical, replacement or unsubstituted C ₆-C ₁₅Aryl formyl radical or replacement or unsubstituted C ₂-C ₁₅The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; The parent that the group that X represents connects is Y, and the parent that the group that Y represents connects is X; Between " X=Y " singly-bound or two key;

3, metal complex part according to claim 2 is characterized in that: among formula Ia, Ib, the Ic,

Z is CH ₂Or

M=0 or 1, n=0 or 1;

During m=1, X is nitrogen, oxygen, methyne, methylene radical, carbonyl; Y is nitrogen, oxygen, replacement or unsubstituted C ₆-C ₁₂Aryl, connection replace or unsubstituted C ₁-C ₈The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₈The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₈Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₁₂Aryl, replacement or unsubstituted C ₂-C ₁₂Heterocyclic radical or replacement or unsubstituted C ₁-C ₈Alkyl; Perhaps Rc, Rd and N atom connect into ring; The parent that the group that X represents connects is Y, and the parent that the group that Y represents connects is X; Between " X=Y " singly-bound or two key;

R ¹Be hydrogen or replacement or unsubstituted C ₆-C ₁₂Aryl;

E is hydrogen, halogen, nitro, C ₁-C ₈Alkyl, C ₁-C ₈Alkoxyl group, C ₆-C ₁₂Aryl, connection C ₁-C ₈The carbonyl of alkyl, connection C ₁-C ₈The carbonyl of alkoxyl group, connection C ₁-C ₈The carbonyl of alkylamino, connection C ₁-C ₈The carbonyl of alkylamino, connection C ₆-C ₁₂The carbonyl of arylamino, connection C ₂-C ₁₂The carbonyl of heterocyclic radical amino, connection replace or unsubstituted C ₁-C ₈The alkylsulfonyl of alkyl amine group; Or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, aryl, C independently ₂-C ₁₂Heterocyclic radical, C ₁-C ₈Alkyl, formyl radical, C ₁-C ₈Alkyl formyl radical, C ₆-C ₁₂Aryl formyl radical, C ₂-C ₁₂Heterocyclic radical formyl radical, replacement or unsubstituted C ₁-C ₈Alkyl sulphonyl, replacement or unsubstituted C ₆-C ₁₂Aryl sulfonyl or replacement or unsubstituted C ₂-C ₁₂The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring;

E ¹Be hydrogen, halogen, nitro, C ₁-C ₈Alkyl, C ₁-C ₈Alkoxyl group, connection C ₁-C ₈The carbonyl of alkylamino, C ₆-C ₁₂Aryl, C ₆-C ₁₂Aryloxy, connection C ₁-C ₈The carbonyl of alkoxyl group or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, C independently ₆-C ₁₂Aryl, C ₂-C ₁₂Heterocyclic radical, C ₁-C ₈Alkyl, formyl radical, C ₁-C ₈Alkyl formyl radical, C ₆-C ₁₂Aryl formyl radical, C ₂-C ₁₂Heterocyclic radical formyl radical, replacement or unsubstituted C ₁-C ₈Alkyl sulphonyl, replacement or unsubstituted C ₆-C ₁₂Aryl sulfonyl or replacement or unsubstituted C ₂-C ₁₂The heterocyclic radical alkylsulfonyl; Perhaps Rc, Rd and N atom connect into ring;

4, metal complex part according to claim 3 is characterized in that: among formula Ia, Ib and the Ic,

Z is CH ₂Or

N=0 or 1;

During n=1, X ¹Be CH ₂Or phenyl; Y ¹Be oxygen or carbonyl;

During m=0, Y is C ₁-C ₄Alkylamino or C ₁-C ₃Alkoxyl group;

During m=1, X is carbonyl, CH ₂, CH or phenmethyl; Y be nitrogen, NH,

C ₁-C ₄Alkoxyl group, C ₅Heterocyclic oxy group or C ₁-C ₃The alkane siloxy; X and Y are singly-bound or two key;

R ¹Phenyl for hydrogen, phenyl or nitro replacement;

R ²Be C ₁-C ₃Alkyl or C ₁-C ₃Alkoxyl group;

R ³Be hydrogen or C ₆Aryl;

E ⁶Be hydrogen, halogen, C ₁-C ₄Alkyl or C ₁-C ₆Alkoxyl group;

5, structural formula is the metal complex of formula IIa, IIb, IIc:

Wherein, M is metal Ru, tungsten or nickel;

L is a kind of complex compound part of giving electronics;

L ¹And L ²Be halogen, RCOO independently ^-Or ArO ^-Negatively charged ion;

L ³Be a kind of complex compound part of giving electronics;

Wherein, Z is CH ₂Or

M=0 or 1, n=0 or 1; During n=0, p=0 or 1; During n=1, p=0;

M, n, X, X ¹, Y, Y ¹, R ¹, R ², R ³, E, E ¹, E ², E ³, E ⁴, E ⁵, E ⁶And E ⁷Definition with claim 1.

6, metal complex according to claim 5 is characterized in that: the structural formula of described L is Formula Il Ia, IIIb, IIIc or IIId:

R ⁸And R ⁹Independently for replacing or unsubstituted C ₁-C ₂₀Alkyl, C ₁-C ₂₀Alkoxyl group, C ₆-C ₂₀Aryl, C ₆-C ₂₀Aryloxy or C ₂-C ₂₀Heterocyclic radical.

7, metal complex according to claim 6 is characterized in that: among the described formula III a, and R ⁴And R ⁵Be aryl; R ⁶And R ⁷Be hydrogen.

8, metal complex according to claim 6 is characterized in that: the structural formula of described L is formula III a, wherein R ⁴And R ⁵Be mesityl, R ⁶And R ⁷Be hydrogen; Or be formula III d, wherein R ⁸And R ⁹Be cyclohexyl.

9, according to each described metal complex of claim 5-8, it is characterized in that: among formula IIa, IIb, the IIc,

Metal M is a ruthenium;

M=0 or 1, n=0 or 1;

L ¹And L ²Be chlorion;

L is IIIa or IIId; Wherein, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸And R ⁹Identical with the definition of claim 6-8 in each;

During n=0, p=0 or 1;

During n=1, p=0, X ¹And Y ¹Be nitrogen, oxygen, sulphur, CH independently ₂, replacement or unsubstituted C ₁-C ₁₅Alkyl, replacement or unsubstituted C ₆-C ₁₅Aryl, replacement or unsubstituted C ₆-C ₁₅Aryloxy, replacement or unsubstituted C ₂-C ₁₅Heterocyclic aryl, carbonyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkyl, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, imino-, replacement or unsubstituted C ₁-C ₁₅Alkyl imido grpup or suc as formula R _cR _dGroup shown in the N-; Wherein, Rc and Rd are hydrogen, replacement or unsubstituted C independently ₆-C ₁₅Aryl, replacement or unsubstituted C ₂-C ₁₅Heterocyclic radical, replacement or unsubstituted C ₁-C ₁₅Alkyl, formyl radical, replacement or unsubstituted C ₁-C ₁₅Alkyl formyl radical, replacement or unsubstituted C ₆-C ₁₅Aryl formyl radical or replacement or unsubstituted C ₂-C ₁₅The heterocyclic radical formyl radical; Perhaps Rc, Rd and N atom connect into ring; X ¹The parent that each group of expression connects is Y ¹, Y ¹The parent that each group of expression connects is X ¹

10, metal complex according to claim 9 is characterized in that among the formula IIa-IIc,

During n=0, p=0 or 1;

R ¹Be hydrogen or replacement or unsubstituted C ₆-C ₁₂Aryl;

11, metal complex according to claim 10 is characterized in that: among the formula IIa-IIc, M is a ruthenium; L is,

Thricyclohexyl phosphorus; L ¹And L ²Be chlorine;

N=0 or 1;

During n=0, p=0 or 1;

During p=1, L ³Be a position and/or the substituted pyridyl ligands of contraposition, the nitrogen-atoms of pyridyl connects parent, and the substituting group of position and contraposition independently is halogen, C between pyridyl ₁-C ₃Alkoxyl group, C ₁-C ₆Alkyl amine group, replacement or unsubstituted C ₆-C ₁₂Aryl;

During n=1, p=0, X ¹Be CH ₂Or phenyl; Y ¹Be oxygen or carbonyl;

During m=0, Y is C ₁-C ₄Alkylamino or C ₁-C ₃Alkoxyl group;

During m=1, X is carbonyl, CH ₂, CH or phenmethyl; Y be nitrogen, NH,

R ¹Be hydrogen, C ₆The phenyl that aryl or nitro replace;

R ²Be C ₁-C ₃Alkyl or C ₁-C ₃Alkoxyl group;

R ³Be hydrogen or C ₆Aryl;

E ⁶Be hydrogen, halogen, C ₁-C ₄Alkyl or C ₁-C ₆Alkoxyl group;

Among the IIa, when n=0, R ²Be hydrogen, halogen, C ₁-C ₄Alkyl or C ₁-C ₄Alkoxyl group.

12, the preparation method of each described metal complex of claim 5-11 is characterized in that: its any method by following four kinds of methods makes:

Method one comprises following three steps:

3) under the protection of inert gas, step 2) the metal complex intermediate that obtains and complex compound ligand i a, Ib or Ic reaction generates metal complex intermediate Va, Vb or Vc; Wherein, Va, Vb or Vc are that L is PPh among IIa, IIb or the IIc ₃The time compound, wherein M, L ¹, L ², Y, Y ¹, R ¹, R ², E, E ¹, E ²And E ³Each is described with claim 5-11;

Method two: with described in the method one Va, Vb or Vc under protection of inert gas respectively with except PPh ₃Outer other generate following metal complex IIa, IIb or IIc for the complex compound ligand L reaction of electronics, wherein, and p=0, M, L, L ¹, L ², Y, Y ¹, R ¹, R ², E, E ¹, E ²And E ³Definition each is described with claim 5-11, but L is not PPh ₃

Method three: IIa, IIb or IIc other complex compound ligand L reactions to electronics under protection of inert gas and except thricyclohexyl phosphorus are generated following metal complex IIa, IIb or IIc; wherein; among IIa, the IIb or IIc as reactant: p=0, M, L ¹, L ², Y, Y ¹, R ¹, R ², E, E ¹, E ²And E ³Definition each is described with claim 5-11, L is a thricyclohexyl phosphorus; Among IIa, the IIb or IIc as resultant: p=0, M, L ¹, L ², Y, Y ¹, R ¹, R ², E, E ¹, E ²And E ³Definition each is described with claim 5-11, but L is not a thricyclohexyl phosphorus;

Method four: under the protection of inert gas, with method one resultant IIa, the IIb described in arbitrary method or IIc and complex compound ligand L of giving electronics to the method three ³Reaction generates IIa, IIb or IIc, wherein, and among the IIa of the resultant of present method, IIb or the IIc: p=1, M, L, L ¹, L ², L ³, Y, Y ¹, R ¹, R ², E, E ¹, E ²And E ³Each is described with claim 5-11.

13, the preparation method of metal complex as claimed in claim 12 is characterized in that:

In the method two, described except PPh ₃It is thricyclohexyl phosphorus that outer other are given the complex compound ligand L of electronics, or

Mes=2,4, the 6-trimethylphenyl.

14, as the preparation method of claim 12 or 13 described metal complexs, it is characterized in that: method one to method three, described L ¹And L ²Be chlorine.

15, as the preparation method of each described metal complex of claim 12～14, it is characterized in that:

In the step 1) of method one, described R ^a, R ^b, R ^c, R ^dAnd R ^eBe hydrogen; Described inorganic strong alkali is one or more in sodium methylate, sodium ethylate, sodium tert-butoxide and the sodium hydrogen; The consumption of described inorganic strong alkali is 1-3 a times of SM-2 molar weight; Described anhydrous organic solvent is one or more in anhydrous methanol, ethanol, the trimethyl carbinol and the tetrahydrofuran (THF); The consumption of described anhydrous organic solvent is 5-30 a times of SM-2 molar weight; The temperature of described reaction is 45-75 ℃;

Step 2 in method one) in, described ML ¹L ²L ₃Be RuCl ₂P (Ph ₃) ₃The temperature of described reaction is-50 ℃ to-85 ℃; Described ML ¹L ²L ₃Consumption be the SM-2 molar weight 0.3-1.0 doubly;

In the step 3) of method one, the temperature of described reaction is-50 ℃ to-85 ℃; The consumption of described complex compound ligand i a, Ib or Ic is 1-3 a times of complex compound intermediate molar weight;

In method two, the temperature of described reaction is 20 ℃ to 75 ℃, is 60 ℃ to 75 ℃ when reacting with complex compound ligand i IIa, is 20 ℃ to 35 ℃ when reacting with complex compound ligand i IId; The consumption of described IIIa or IIId is complex compound intermediate Va, Vb or Vc molar weight 1-3 a times;

In method four, the temperature of described reaction is 20 ℃ to 35 ℃, described L ³Consumption be complex compound II molar weight 1-5 doubly;

To step 3), and method two is to method four in the step 1) of method one, the time of reaction all with detection reaction fully till.

16, according to each described metal complex part of claim 1-4, it is characterized in that: described heterocyclic radical is a heterocyclic aryl.

17, according to claim 5, each described metal complex of 9-11, it is characterized in that: described heterocyclic radical is a heterocyclic aryl.

18, each described metal complex of claim 5-11 is made Application of Catalyst in the olefin metathesis replacement(metathesis)reaction.

19, application according to claim 18 is characterized in that: the olefin metathesis replacement(metathesis)reaction that described olefin metathesis replacement(metathesis)reaction is an intramolecular cyclization, intermolecular olefin metathesis replacement(metathesis)reaction or the reaction of intermolecular cycloolefin ring opening metathesis polymerization.

20, application according to claim 19 is characterized in that: the described cycloolefin of polyreaction that is used for is for having tensile cycloolefin structure or polycyclic olefin structure; They are structures of replacement or non-replacement, and they contain F, Cl, Br, N, O, Si, S, P, B, C in one or more rings ₆-C ₁₅Aromatic series and C ₄-C ₁₅In the aromatic heterocycle substituting group one or more.

21, application according to claim 20 is characterized in that: described cycloolefin structure contains 4 or 5 or 7-16 carbon atom, or a plurality of heteroatoms or heteroatom group.

22, application according to claim 20 is characterized in that: described polycyclic olefin structure is the polycyclic olefin structure that contains 2 to 6 rings.

23, according to the application described in the claim 20, it is characterized in that: described polycyclic olefin is that one or more hydrogen in cyclopentadiene or its molecule are by C ₁-C ₁₅Saturated or undersaturated alkyl, replacement or unsubstituted C ₁-C ₁₅Amido, replacement or unsubstituted C ₁-C ₁₅Alkoxyl group, replacement or unsubstituted C ₆-C ₁₅Aryloxy, replacement or unsubstituted C ₁-C ₁₅Heterocyclic oxy group, replacement or unsubstituted C ₁-C ₁₅Alkylthio, replacement or unsubstituted C ₆-C ₁₅Arylthio, connection replace or unsubstituted C ₁-C ₁₅The carbonyl of alkoxyl group, methanoyl, formamido-, replacement or unsubstituted C ₁-C ₁₅Alkyl carbonyloxy, replacement or unsubstituted C ₁-C ₁₅Alkyl formamides base, replacement or unsubstituted C ₆-C ₁₅Aryl methanoyl or replacement or unsubstituted C ₆-C ₁₅The derivative that the aryl carboxamides base replaces.

24, according to the application described in the claim 22, it is characterized in that: described polycyclic olefin is following polycyclic olefin structure VIa and VIb:

Wherein:

25, according to the application described in the claim 22, it is characterized in that: described polycyclic olefin is following polycyclic olefin structure VIIa-VIIb:

Wherein:

26, application according to claim 19 is characterized in that: described intermolecular cycloolefin ring opening metathesis polymerization reaction is the polyreaction of preparation macromolecule polymer material.

27, application according to claim 26 is characterized in that: the organic solvent of the polyreaction of described preparation macromolecule polymer material is one or more in methylene dichloride, ethylene dichloride, chloroform, toluene, dimethylbenzene, chlorobenzene and the ionic liquid.

28, application according to claim 26 is characterized in that: in the described intermolecular cycloolefin ring opening metathesis polymerization reaction, when raw material cycloolefin or polycyclic olefin are liquid, do not add organic solvent.

29, application according to claim 26 is characterized in that: described high molecular polymer is suc as formula shown in VIc, VId, VIe, VIIc, VIId, the Poly-DCPD;

30, application according to claim 29 is characterized in that: in formula VIc, VId, VIe, VIIc, VIId, Poly-DCPD,

31, application according to claim 30 is characterized in that: in formula VIc, VId, VIe, VIIc, VIId, Poly-DCPD,

32, a kind of suc as formula the high molecular polymer shown in VIc, VId, VIe, VIIc, VIId and the Poly-DCPD;

33, high molecular polymer according to claim 32 is characterized in that: in formula VIc, VId, VIe, VIIc, VIId, Poly-DCPD,

34, high molecular polymer according to claim 33 is characterized in that: in formula VIc, VId, VIe, VIIc, VIId, Poly-DCPD,

35,, it is characterized in that it is made by in following two kinds of methods any according to the preparation method of each described high molecular polymer of claim 32-34:

Under the protection of inert gas, each described metal complex catalyst of raw material monomer and claim 5-11 carries out reacting by heating, can make VIc, VId, VIe, VIIc, VIId or Poly-DCPD;

Under the protection of inert gas, in the anhydrous organic solvent, each described metal complex catalyst of raw material monomer and claim 5-11 progressively is warming up to 75 ℃ of reactions from 20 ℃, can make VIc, VId, VIe, VIIc, VIId or Poly-DCPD.

36, the preparation method of high molecular polymer according to claim 35 is characterized in that: in described method one: catalyst consumption is the 0.5%-10% of raw material monomer molar weight, and the temperature of reacting by heating is 30-120 ℃; In described method two: catalyst consumption is the 0.01%-5% of raw material monomer molar weight, and anhydrous organic solvent is an ethylene dichloride.

37, according to the application of each described high molecular polymer of claim 32-34 in effective carrier, tooth patching material, high molecule liquid crystal material, conductive polymer novel material, system film or the spinning material of the explosion-proof lamp for preparing high strength and high rigidity, tire material, polymer medicament prodrug.