CN106543232B

CN106543232B - Metal bridge location fused ring compound and its preparation method and application

Info

Publication number: CN106543232B
Application number: CN201510606889.2A
Authority: CN
Inventors: 夏海平; 卓庆德; 林剑锋; 周小茜; 卓凯玥; 何旭敏; 张弘
Original assignee: Xiamen University
Current assignee: Xiamen University
Priority date: 2015-09-22
Filing date: 2015-09-22
Publication date: 2019-01-11
Anticipated expiration: 2035-09-22
Also published as: CN106543232A

Abstract

The present invention relates to organic chemistry and Organometallic Chemistry field, a kind of metal bridge location fused ring compound and its preparation method and application is disclosed.Metal bridge location fused ring compound provided by the invention is with structure shown in any one in Formulas I-VI and I'-VI'.The present invention also provides the preparation methods of the metal bridge location fused ring compound and the application in solar battery, photodynamic therapy, photocatalytic water, lithium-air battery field.The main structure of metal bridge location fused ring compound provided by the invention has good flatness, it is a big conjugated system, with armaticity, stability is good, with good UV-visible-near infrared absorption and preferable chemical property, thus it can be widely applied to the fields such as solar battery, photodynamic therapy, photocatalytic water and lithium-air battery.

Description

Metal bridge location fused ring compound and its preparation method and application

Technical field

The present invention relates to organic chemistry and Organometallic Chemistry field, and in particular, to a kind of metal bridge location annelation conjunction Object and its preparation method and application.

Background technique

Organometallic Chemistry is to study the chemistry containing carbon-to-metal bond, is the metal-organic synthesis of research, knot Structure, reaction, bonding, performance and a front subject of application.As an important branch subject of chemistry, with the energy, material Material, environment are closely related with life science, become one of the Disciplinary Frontiers of modern age chemistry.

The miscellaneous aromatic fused ring compound of transition metal is a kind of important metallo-organic compound, phase on this kind of compound form When in the carbon atom on organic condensed ring skeleton replaced metal obtained from product.In the miscellaneous fused ring compound of metal, metal Multiple aromatic rings conjugation can be simultaneously participated in, the performance of compound can be significantly improved.In recent years, the miscellaneous aromatic fused ring of transition metal The synthesis for closing object is widely paid close attention to characterization by people.

2013, it is miscellaneous thick that Xia etc. (Nat.Chem.2013,5,698-703) reports a kind of novel metal bridge location metal Cycle compound --- osmium miscellaneous penta takes alkine compounds, which has aggregation fluorescence enhancement, big Stock displacement, luminescent lifetime long The features such as, it is with important application prospects in light, electrical domain.2014, Xia etc. reported the miscellaneous condensed ring of osmium of a kind of metal bridge location Compound, such compound have good UV-Vis absorption properties (Angew.Chem.Int.Ed.2014,53, 6232-6236).2015, Xia etc. reported the miscellaneous fused ring compound of osmium of another kind of metal bridge location again, with good light Acoustic imaging and light thermal property have potential application prospect in the diagnosing and treating of tumour (Angew.Chem.Int.Ed.2015,54,6181-6185)。

However, although the miscellaneous aromatic fused ring compound of metal bridge location metal shows many other materials not in light, electrical domain The special performance having, but the compound of this type is also seldom at present, therefore, development and composite structure multiplicity, type are rich The miscellaneous fused ring compound of metal rich, that stability is high is particularly important.

Summary of the invention

In order to provide a kind of compound with good light, electrical property, meet solar battery, photodynamic therapy, light Application in the fields such as Xie Shui and lithium-air battery, the invention proposes a kind of metal bridge location fused ring compound and its preparation sides Method and purposes.

The present inventor is after studying it was unexpectedly observed that metallic atom Ru, Rh and Ir are located at bridge location fused ring compound Multiple rings center when, it is one that the main structure of the metal bridge location fused ring compound of formation, which has good flatness, Big conjugated system, entire molecule have armaticity, and stability is good.The increase of simultaneous conjugated system, metal bridge location are thick The gradually red shift of the absorption spectrum of cycle compound, and have in ultraviolet-visible-near-infrared wideband absorption spectrum and preferable electrification Performance is learned, therefore can be widely applied to the fields such as solar battery, photodynamic therapy, photocatalytic water and lithium-air battery, thus Complete the present invention.

According to the first aspect of the invention, the present invention provides a kind of metal bridge location fused ring compound, compound tools There is structure shown in any one in Formulas I-VI and I'-VI':

Wherein,

In Formulas I, III, IV, I', III' and IV', [M]¹For RuAL₂、RhL₂Or IrL₂；

In Formula II and II', [M]²For RuL₃、RhAL₂Or IrAL₂；

In Formula V and V', [M]³For RuL₂, RhAL or IrAL；

In Formula IV and VI', [M]⁴For RuA₂L, RhAL or IrAL；

Wherein,

A is any one in-H, halogen ,-SCN and-CN；

L is Phosphine ligands, CO ligand, pyridine, nitrogen heterocycle carbine ligand, nitrile ligand and isocyanide class bielectron ligand At least one of；

R₁ ⁺Cationic substituent in any one in position to indicate digital 1-6 on Formulas I-VI, and R₁ ⁺For The quaternary ammonium cation of 3-30 carbon atom quaternary phosphine cation or 3-24 carbon atom；

R₂For at least one of position for indicating digital 1-9 on Formulas I-VI, and and R₁ ⁺Position is different Substituent group；

R₃For the substituent group at least one of position for indicating digital 1-9 on Formulas I '-VI'；

R₂And R₃Respectively independently selected from-H, halogen ,-SCN ,-CN, alkyl, alkoxy, the alkane sulphur of 1-20 carbon atom Base, acyl group, ester group, amido, amide groups, carboxyl, the amide groups of 2-20 substituted carbon atom, the cycloalkanes of 3-20 carbon atom Base, substituted or unsubstituted aryl, the alkenyl of substituted or unsubstituted 2-20 carbon atom, substituted or unsubstituted 2-20 carbon The alkynyl of atom, aryloxy group, the arylthio of 1-20 carbon atom, and any one in water-soluble substituent group can be improved；

In formula III and III', X is-CR₅R₆-、-NR₇,-O-, any one in-S- and-Se-；

In Formula V and V', Y is-NR₇, any one in-O- and-S-；

Wherein, R₄、R₅And R₆The range and R of the substituent group of selection₂Or R₃It is identical, R₇For substituted or unsubstituted aryl, take Generation or unsubstituted 1-20 carbon atom alkyl and 3-20 carbon atom naphthenic base in any one；

In Formulas I-VI, Z^-For Cl^-、Br^-、I^-、BF₄ ^-、CF₃SO₃ ^-、CH₃COO^-、(CF₃SO₂)₂N^-、NO₃ ^-、ClO₄ ^-、PF₆ ^-With BPh₄ ^-In any one.

According to the second aspect of the invention, the present invention provides the preparation method of above-mentioned metal bridge location fused ring compound, This method comprises:

Using Formula VII compound represented and ruthenium complex by cycloaddition reaction preparation as [M]¹For RuAL₂When Formulas I institute The compound shown；Preparation is reacted in organic solvent as [M] with alkali 1 using Formula II compound represented¹For RhL₂Or IrL₂Up-to-date style I compound represented；

[M] is worked as by cycloaddition reaction preparation with rhodium complex and complex of iridium respectively using Formula VII compound represented² For RhAL₂Or IrAL₂When Formula II compound represented；Add alternatively, nucleophilic occurs with nucleopilic reagent using Formulas I compound represented At reaction preparation formula II compound represented；

Using Formulas I compound represented withNucleophilic addition preparation occurs when X isUp-to-date style III compound represented；Pass through ring with ruthenium complex, rhodium complex and complex of iridium respectively using Formula VIII compound represented Addition reaction preparation is-CR as X₅R₆When formula III compound represented；It is reacted using Formulas I compound represented with water or oxygen Preparation formula III compound represented when X is-O-；Use Formulas I compound represented and H₂S, at least one of NaHS and S Reaction preparation formula III compound represented when X is-S-；When to react with Se preparation X using Formulas I compound represented be-Se- Formula III compound represented；Use Formulas I compound represented and R₇NH₂Reaction preparation X is-NR₇When formula III shown in Compound；

Pass through chemical combination shown in cycloaddition reaction preparation formula IV using Formula X compound represented and Formulas I compound represented Object；

Pass through chemical combination shown in ring expansion preparation formula V using Formula XI compound represented and formula III compound represented Object；

Pass through cycloaddition reaction system with ruthenium complex, rhodium complex and complex of iridium respectively using Formula IX compound represented Standby Formula IV compound represented；

It is hydrolyzed in the aqueous solution of alkali 2 using Formulas I compound represented and carrys out preparation formula I' compound represented.

Nucleophilic addition preparation formula II' compound represented occurs using Formulas I ' compound represented and nucleopilic reagent； Carry out preparation formula II' compound represented alternatively, hydrolyzing in the aqueous solution of alkali 2 using Formula II compound represented；

Using Formulas I ' compound represented withNucleophilic addition preparation occurs when X isUp-to-date style III' compound represented；Preparation is reacted when X is shown in-O- up-to-date style III' with water or oxygen using Formulas I ' compound represented Compound；Use Formulas I ' compound represented and H₂S, it is-S- up-to-date style III' that X is worked as at least one of NaHS and S reaction preparation Compound represented；Preparation is reacted when X is-Se- up-to-date style III' compound represented with Se using Formulas I ' compound represented；Make With Formulas I ' compound represented and R₇NH₂Reaction preparation X is-NR₇When formula III ' compound represented；Alternatively, using formula III Compound represented hydrolyzes in the aqueous solution of alkali 2 carrys out preparation formula III' compound represented；

Using Formula X compound represented and Formulas I ' compound represented by changing shown in cycloaddition reaction preparation formula IV' Close object；Or it is hydrolyzed in the aqueous solution of alkali 2 using formula IV compound represented and carrys out preparation formula IV' compound represented；

Using Formula XI compound represented and formula III ' compound represented by changing shown in ring expansion preparation formula V' Close object；Or it is hydrolyzed in the aqueous solution of alkali 2 using Formula V compound represented and carrys out preparation formula V' compound represented；

It is hydrolyzed in the aqueous solution of alkali 2 using Formula IV compound represented and carrys out preparation formula VI' compound represented；

Wherein, in Formula VII-XI,

G is-O- ,-S- ,-CR₁₈R₁₉-、-SiR₂₀R₂₁And-NR₂₂In any one；

Wherein, R₁₈、R₁₉、R₂₀、R₂₁And R₂₂It is separately hydrogen, alkyl, the 1-20 carbon atom of 1-20 carbon atom Ester group, the acyl group of 1-20 carbon atom, the naphthenic base of 3-20 carbon atom, 1-20 carbon atom halogenated alkyl, itrile group, nitre Base, substituted or unsubstituted aryl andIn any one；Wherein, R₂₃For C₁-C₈Alkyl and substituted or unsubstituted Any one in phenyl；

R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃、R₁₄、R₁₅、R₁₆And R₁₇The range and R for the substituent group that can be selected₂Or R₃It is identical；

M and n is respectively the integer of 1-6, and m+n < 8；

The ruthenium complex is RuCl₂(PPh₃)₃、RuCl₂(PMe₃)₃、RuCl₂(PEt₃)₃And RuCl₂(PCy₃)₃In extremely Few one kind；

The rhodium complex is RhCl (PPh₃)₃、RhHCl₂(PPh₃)₃、RhCl(PMe₃)₃、RhCl(PEt₃)₃And RhCl (PCy₃)₃At least one of；

The complex of iridium is IrHCl₂(PPh₃)₃、IrCl(PPh₃)₃、IrCl(PMe₃)₃、IrCl(PEt₃)₃And IrCl (PCy₃)₃At least one of；

The alkali 1 is the carbonate and/or hydride of alkali metal；

The alkali 2 is the hydroxide of alkali metal；

The nucleopilic reagent is halogen simple substance, the alcohol of 1-10 carbon atom, sodium alkoxide, potassium alcoholate, mercaptan, sodium mercaptides, mercaptan potassium, At least one of phenol, phenol sodium and phenol potassium.

According to the third aspect of the present invention, the present invention provides above-mentioned metal bridge location fused ring compounds in solar-electricity Pond, photodynamic therapy, photocatalytic water, the application in lithium-air battery field.

The main structure of metal bridge location fused ring compound provided by the invention has good flatness, is a big conjugation System has armaticity, and stability is good, has good UV-visible-near infrared absorption and preferable electrochemistry Can, thus can be widely applied to the fields such as solar battery, photodynamic therapy, photocatalytic water and lithium-air battery.

Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.

Detailed description of the invention

Fig. 1 is the UV-visible absorption spectrum of the metal bridge location fused ring compound I-1 in test case 1 of the present invention.

Fig. 2 is the UV-visible absorption spectrum of the metal bridge location fused ring compound II-1 in test case 2 of the present invention.

Fig. 3 is the UV-visible absorption spectrum of the metal bridge location fused ring compound II-11 in test case 2 of the present invention.

Fig. 4 is circulation-volt-ampere curve of the metal bridge location fused ring compound II-2 in test case 3 of the present invention.

Fig. 5 is charging potential shadow of the metal bridge location fused ring compound II-2 in test case 3 of the present invention to lithium-air battery Ring situation curve.

Fig. 6 is the UV-visible absorption spectrum of the metal bridge location fused ring compound IV-1 in test case 4 of the present invention.

Fig. 7 is the external activity oxygen test result of the metal bridge location fused ring compound IV-1 in test case 4 of the present invention.

Fig. 8 is the UV-visible absorption spectrum of the metal bridge location fused ring compound V-3 in test case 5 of the present invention.

Fig. 9 is the UV-visible absorption spectrum of the metal bridge location fused ring compound VI-1 in test case 6 of the present invention.

Figure 10 is the UV-visible absorption spectrum of the metal bridge location fused ring compound III-9 in test case 7 of the present invention.

Figure 11 is the UV-visible absorption spectrum of the metal bridge location fused ring compound I'-6 in test case 8 of the present invention.

Figure 12 is the UV-visible absorption spectrum of the metal bridge location fused ring compound II'-9 in test case 9 of the present invention.

Figure 13 is the uv-visible absorption spectra of the metal bridge location fused ring compound III'-4 in test case 10 of the present invention Figure.

Figure 14 is the UV-visible absorption spectrum of the metal bridge location fused ring compound IV'-5 in test case 11 of the present invention.

Figure 15 is the UV-visible absorption spectrum of the metal bridge location fused ring compound V'-1 in test case 12 of the present invention.

Figure 16 is the uv-visible absorption spectra of the metal bridge location fused ring compound VI'-11 in test case 13 of the present invention Figure.

Specific embodiment

Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

Wherein,

In Formulas I, III, IV, I', III' and IV', [M]¹For RuAL₂、RhL₂Or IrL₂；

In Formula II and II', [M]²For RuL₃、RhAL₂Or IrAL₂；

In Formula V and V', [M]³For RuL₂, RhAL or IrAL；

In Formula IV and VI', [M]⁴For RuA₂L, RhAL or IrAL；

Wherein, A is any one in-H, halogen ,-SCN and-CN；

The halogen is any one in-F ,-Cl ,-Br and-I.

Wherein, L can be but be not limited to Phosphine ligands, CO ligand, pyridine, N-heterocyclic carbine (N- At least one of Heterocyclic Carbenes NHC) ligand, nitrile ligand and isocyanide class bielectron ligand.

The Phosphine ligands can be 3-24 carbon atom, preferably 5-20 carbon atom, the alkane of more preferable 6-18 carbon atom Base phosphine, naphthenic base phosphine and aryl phosphine.Preferably, the Phosphine ligands are trimethyl-phosphine, triethyl phosphine, tripropyl phosphine, triisopropyl Any one in phosphine, tri-tert-butylphosphine, tricyclohexyl phosphine and triphenylphosphine.

The pyridine is the ligand containing pyridine or bipyridyl structural unit.Preferably, the pyridine For picoline, ethylpyridine, 1,4- bipyridyl, 1,2- bis- (4- pyridyl group) ethylene, vinylpyridine, ethynyl pyridine, pyrrole Pyridine boric acid, aminopyridine, cyanopyridine, mercaptopyridine, dimethylamino pyridine, phenylpyridine and bis- (4- pyridyl group) ethane of 1,2- In any one.

The nitrogen heterocycle carbine ligand can be any ligand containing N-heterocyclic carbine structural unit.Preferably, described Nitrogen heterocycle carbine ligand is imidazole type N-heterocyclic carbine, imidazoline type N-heterocyclic carbine, thiazole type N-heterocyclic carbine and triazole type Any one in N-heterocyclic carbine.

The nitrile ligand is the ligand containing itrile group structural unit.Preferably, the nitrile ligand be acetonitrile, propionitrile and Any one in cyanophenyl.

The isocyanide class bielectron ligand is the ligand containing isocyano group structural unit.Preferably, the double electricity of the isocyanide class Sub- ligand is any one in cyclohexyl isocyanide, tert-butyl isocyanide and phenyl isocyanide.

Wherein, L₂It can be considered an entirety.Preferably, L₂To match selected from bidentate nitrogen ligands, bidentate phosphine ligands, bidentate carbon-to-nitrogen Any one in body and bidentate oxygen-nitrogen ligand.

The bidentate nitrogen ligands refer to the ligand using bidentate nitrogen-atoms as coordination atom.The bidentate nitrogen ligands for example may be used Think any one in ethylenediamine, 2,2'- bipyridyl and 1,10- phenanthroline.

The bidentate phosphine ligands refer to the ligand using bidentate phosphorus atoms as coordination atom.The bidentate phosphine ligands for example may be used Think DPPM (Bis- (diphenylphosphino) methane, 1,1- bis- (diphenylphosphine) methane), DPPE (1,2-Bis (diphenylphosphino) ethane, 1,2- bis- (diphenylphosphine) ethane and DPPP (1,3-Bis (diphenylphosphino) propane, any one in 1,3- bis- (diphenylphosphine) propane.

The bidentate carbon-to-nitrogen ligand refers to the ligand using bidentate carbon-to-nitrogen atom as coordination atom.The bidentate carbon-to-nitrogen Ligand can be for example adjacent phenylpyridine.

Bidentate oxygen-the nitrogen ligand refers to the ligand using bidentate oxygen-nitrogen-atoms as coordination atom.Bidentate oxygen-the nitrogen Ligand for example can be 8-hydroxyquinoline.

Wherein, AL₂It can be considered an entirety.Preferably, AL₂For terpyridyl or three tooth Pincer (pincer) ligands.

The three teeth Pincer ligand can be pincer ligand.The pincer ligand for example can for PPP, PNP, PCP, Any one in NNN, NCN, NPN, ONO, OPO, OCO, SCS and CCC.

R₁ ⁺To indicate digital 1-6 on Formulas I-VI, preferably indicating digital 2-6, the more preferable position for indicating number 2 and 5 In any one on cationic substituent, and R₁ ⁺For 3-30 carbon atom, preferably 5-23 carbon atom, more preferable 6-18 Carbon atom quaternary phosphine cation or 3-24 carbon atom, preferably 5-20 carbon atom, the quaternary ammonium of more preferable 6-18 carbon atom are positive Ion.

The quaternary phosphine cation can for alkyl quaternary phosphine, naphthenic base season phosphine and aryl season phosphine cation in any one. Preferably, the quaternary phosphine cation is trimethyl-phosphine, triethyl phosphine, tripropyl phosphine, tri isopropyl phosphine, tri-tert-butylphosphine, tricyclic Hexyl phosphine and triphenylphosphine cation in any one.

The quaternary ammonium cation is Trimethylamine, triethylamine, one ethylamine of dimethyl, tripropyl ammonium, triisopropyl ammonium With any one in tri-tert ammonium cation.

R₂For at least one of position for indicating digital 1-9 on Formulas I-VI, and and R₁ ⁺Position is different Substituent group.Preferably, R₂On at least one of position to indicate number 1,2,3,4,5,6,8 and 9 on Formulas I-VI, and With R₁ ⁺The different substituent group in position.It is further preferred that R₂To indicate number 1,4,5,6,8 and 9 on Formulas I-VI On at least one of position, and and R₁ ⁺The different substituent group in position.

R₃For the substituent group at least one of position for indicating digital 1-9 on Formulas I '-VI'.Preferably, R₃For The substituent group at least one of position of number 1,2,3,4,5,6,8 and 9 is indicated on Formulas I '-VI'.Further preferably Ground, R₃The substituent group at least one of position to indicate number 1,4,5,6,8 and 9 on Formulas I '-VI'.

R₂And R₃It can be separately selected from-H, halogen ,-SCN ,-CN, 1-20 carbon atom, preferably 1-17 carbon are former Alkyl, alkoxy, alkylthio group, acyl group, ester group, amido, amide groups, the carboxyl of sub, more preferable 1-8 carbon atom, substituted 2- The amide groups of 20 carbon atoms, preferably 2-17 carbon atom, more preferable 2-8 carbon atom, 3-20 carbon atom, preferably 3-17 The naphthenic base of carbon atom, more preferable 3-8 carbon atom, substituted or unsubstituted aryl, substituted or unsubstituted 2-20 carbon are former The alkenyl of son, preferably 2-17 carbon atom, more preferable 2-8 carbon atom, substituted or unsubstituted 2-20 carbon atom, preferably 2- The alkynyl of 17 carbon atoms, more preferable 2-8 carbon atom, 1-20 carbon atom, preferably 2-17 carbon atom, more preferable 2-8 Aryloxy group, the arylthio of carbon atom, and at least one of water-soluble substituent group can be improved.

Wherein, the halogen can be any one in-F ,-Cl ,-Br and-I.

The alkyl of the 1-20 carbon atom can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, secondary Butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-amyl, tertiary pentyl, n-hexyl, isohesyl, new hexyl, Sec-Hexyl, uncle Hexyl, n-heptyl, different heptyl, new heptyl, Zhong Gengji, tertiary heptyl, n-octyl, iso-octyl, new octyl, secondary octyl, t-octyl, just Dodecyl, n-hexadecyl, n-octadecane base, n-eicosane base, WithIn any one.

The alkoxy of the 1-20 carbon atom can be methoxyl group, ethyoxyl, positive propoxy, isopropoxy, positive fourth oxygen Base, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, neopentyl oxygen, secondary amoxy, tertiary amoxy, just Hexyloxy, dissident's oxygroup, new hexyloxy, secondary hexyloxy, tertiary hexyloxy, positive oxygroup in heptan, different oxygroup in heptan, new oxygroup in heptan, Zhong Geng oxygen Base, tertiary oxygroup in heptan, n-octyloxy, different octyloxy, new octyloxy, secondary octyloxy, tertiary octyloxy, n-dodecane oxygroup, positive 16 Any one in alkoxy, n-octadecane oxygroup and n-eicosane oxygroup.

The alkylthio group of the 1-20 carbon atom can be methyl mercapto, ethylmercapto group, positive rosickyite base, isopropyisulfanyl, positive fourth sulphur Base, isobutylthio, secondary butylthio, tertiary butylthio, positive penta sulfenyl, isopentylthio, new penta sulfenyl, secondary penta sulfenyl, tertiary penta sulfenyl, just Own sulfenyl, isohexylthio, new own sulfenyl, secondary own sulfenyl, tertiary own sulfenyl, positive sulfenyl in heptan, different sulfenyl in heptan, new sulfenyl in heptan, Zhong Geng sulphur Base, tertiary sulfenyl in heptan, just pungent sulfenyl, different pungent sulfenyl, new pungent sulfenyl, Zhong Xin sulfenyl, tertiary pungent sulfenyl, n-dodecane sulfenyl, positive 16 Any one in alkylthio group, n-octadecane sulfenyl and n-eicosane sulfenyl.

The acyl group of the 1-20 carbon atom can be WithIn any one.

The ester group of the 1-20 carbon atom refers to that the total number of carbon atoms between 1-20, and contains ester bondUnivalent perssad.For example, the ester group of the 1-20 carbon atom can be In any one.

The amido of the 1-20 carbon atom can be methylamino, ethylamino-, Propylamino, butylamine base, amylamine base, hexylamine Base, heptyl amice base, octylame base, dimethylamino (NMe₂), diethylin (NEt₂), dipropyl amido, dibutyl amino, n-dodecylamine base, just Any one in cetylamine base, octadecyl amine base and positive 20 amido.

The amide groups of the 1-20 carbon atom refers to that the total number of carbon atoms between 1-20, and contains amido bondUnivalent perssad.For example, the amide groups of the 1-20 carbon atom can be In Any one.

The carboxyl of the 1-20 carbon atom refers to that the total number of carbon atoms between 1-20, and containsMonovalence Group.For example, the carboxyl can be With In any one.

The amide groups of the 2-20 substituted carbon atom refers to the amido bond in above-mentioned amide groupsOn Shape after the H being connected with N atom is replaced by the alkyl of 1-20 carbon atom, preferably 1-17 carbon atom, more preferable 1-8 carbon atom At substituent group.Alkyl and the above-mentioned phase of the 1-20 carbon atom, preferably 1-17 carbon atom, more preferable 1-8 carbon atom Together.

For example, the amide groups of the 2-20 substituted carbon atom can be WithIn any one.

The naphthenic base of the 3-20 carbon atom can be pungent for cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring Any one in base, cyclo-dodecyl, ring cetyl, ring octadecyl and ring eicosyl.

The aryl can be in phenyl, naphthalene, anthryl, phenanthryl, pyrenyl, thienyl, furyl, pyridyl group and pyrrole radicals Any one.

Substituent group on the substituted aryl can be 1-20 carbon atom, preferably 1-17 carbon atom, more preferable 1- Alkyl, alkoxy, alkylthio group, acyl group, ester group, amido, amide groups, the carboxyl of 14 carbon atoms, 2-20 substituted carbon atom, It is 3-20 carbon atom, preferably 3-17 carbon atom, more excellent it is preferred that the amide groups of 2-17 carbon atom, more preferable 2-8 carbon atom Select the naphthenic base of 3-8 carbon atom, 2-20 carbon atom, preferably 2-17 carbon atom, more preferable 2-14 carbon atom alkenyl, Alkynyl, nitro, at least one of cyano and halogen.

Wherein, alkyl, alkoxy, alkylthio group, acyl group, ester group, amido, amide groups, the carboxyl of the 1-20 carbon atom, The amide groups of 2-20 substituted carbon atom, the naphthenic base of 3-20 carbon atom, the alkenyl of 2-20 carbon atom, alkynyl with it is above-mentioned It is identical.

Preferably, the substituted aryl is In any one.

The alkenyl of the 2-20 carbon atom for example can be WithIn any one.

The alkynyl of the 2-20 carbon atom can be WithIn any one.

Substituent group in the substituted alkenyl and substituted alkynyl can be 3-20 carbon atom, preferably 3-17 carbon original Any one in the alkyl of sub, more preferable 3-8 carbon atom, naphthenic base and substituted or unsubstituted aryl.

Wherein, the alkyl, naphthenic base and substituted or unsubstituted aryl are same as described above.

Substituent group in the substituted alkenyl and substituted alkynyl for example can be methyl, ethyl, n-propyl, isopropyl Base, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-amyl, tertiary pentyl, n-hexyl, dissident Base, new hexyl, Sec-Hexyl, tertiary hexyl, n-heptyl, different heptyl, WithIn any one.

The substituted alkenyl for example can be WithIn any one.

The substituted alkynyl for example can be WithIn any one.

The aryloxy group of the 1-20 carbon atom is that the monovalence that above-mentioned aryl or substituted aryl and oxygen atom are connected to form takes Dai Ji.For example, the aryloxy group can for phenoxy group (- OPh), naphthoxy, anthracene oxygroup, luxuriant and rich with fragrance oxygroup, pyrene oxygroup, thiophene oxy, Furans oxygroup, pyridine oxygroup, pyrroles's oxygroup, p- toloxyl, m- toloxyl, oxy-o-cresyl, p- nitro-phenoxy and Any one in p- methoxyphenoxy.

The arylthio of the 1-20 carbon atom is that the monovalence that above-mentioned aryl or substituted aryl and sulphur atom are connected to form takes Dai Ji.For example, the arylthio can for thiophenyl (- SPh), naphthalene sulfenyl, anthracene sulfenyl, luxuriant and rich with fragrance sulfenyl, pyrene sulfenyl, thiophene thio, Furansulfenyl, pyridine thio, pyrroles's sulfenyl, p- Tolylsulfanvl, m- Tolylsulfanvl, adjacent Tolylsulfanvl, p- nitrophenylsulfenyl and Any one in p- Methoxv-phenylsulfanvl.

It can be polyethylene glycol residue, hyaluronic acid residue, polyacrylic acid and sugar that the energy, which improves water-soluble substituent group, Any one in analog derivative residue.

The polyethylene glycol residue refers to that the hydroxyl on one of end of polyethylene glycol removes remaining part after H.

The weight average molecular weight of the polyethylene glycol can be 200-200000.

The hyaluronic acid residue refers to the D-Glucose aldehydic acid of hyaluronic acid or any one hydroxyl of N-acetyl-glucosamine The carboxyl that base removes the D-Glucose aldehydic acid of remaining part or hyaluronic acid after H removes hydroxyl (- OH) remainder afterwards.

The weight average molecular weight of the hyaluronic acid can be 2000-2000000.

The carbohydrate derivative residue refers to that any one hydroxyl of carbohydrate derivative removes remaining part after hydrogen atom.

The carbohydrate derivative can be the derivative of glucose, sucrose, maltose, galactolipin, lactose, fructose and sialic acid Any one in object.The carbohydrate derivative for example can be glucuronic acid, glucose acetal, glucose hemiacetal and carboxylic Any one in methyl lactose.

It should be noted that in the present invention, substituent R₂And R₃It all can be one or more；It is same if it is multiple Multiple R on a molecule₂And R₃Respectively can be identical or different, just in the above range.

Compound according to the present invention, in Formulas I-VI and I'-VI', indicate digital 1-8 the position 1,2-, 2,3- Set, at least one of at the position 3,4-, the position 4,5-, the position 5,6- and the position 7,8- on can substituted or unsubstituted ring Shape substituent group.Preferably, the position 2,3- and/or 4, can substituted or unsubstituted cyclic substituents at the position 5-.

The cyclic substituents can be but be not limited to the three-membered ring being all made of carbon atom, four-membered ring, five-membered ring, six Member ring, heptatomic ring or octatomic ring substituent group, or the ternary by being formed containing at least one hetero atom in aerobic, sulphur, nitrogen and silicon Ring, four-membered ring, five-membered ring, hexatomic ring, heptatomic ring or octatomic ring substituent group.

The substituent group of the substituted cyclic substituents can be the alkyl of 1-20 carbon atom, the ester of 1-20 carbon atom Base, the acyl group of 1-20 carbon atom, the carboxyl of 1-20 carbon atom, substituted or unsubstituted aryl, 3-8 carbon atom cycloalkanes Base, itrile group, nitro andAt least one of.

Wherein, the R₃₀It can be the alkane of 1-20 carbon atom, preferably 1-17 carbon atom, more preferable 1-14 carbon atom Any one in base and substituted or unsubstituted phenyl.The alkyl of the 1-20 carbon atom is same as described above.The substitution Or the substituent group in unsubstituted phenyl is identical as the substituent group on above-mentioned substituted aryl.Preferably, the substituted phenyl In substituent group be 1-20 carbon atom alkyl or halogen.Preferably,For WithIn it is any It is a kind of.

The alkyl of the 1-20 carbon atom, the ester group of 1-20 carbon atom, 1-20 carbon atom acyl group, 1-20 carbon The carboxyl of atom, substituted or unsubstituted aryl are same as described above.

The naphthenic base of the 3-8 carbon atom can be pungent for cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl and ring Any one in base.

The substituted or unsubstituted cyclic substituents for example can be WithIn any one.

In formula III and III', X can be-CR₅R₆-、-NR₇, it is-O-, any one in-S- and-Se- Kind.

Wherein, R₄、R₅And R₆The range and R for the substituent group that can be selected₂Or R₃It is identical.

R₇It can be former for substituted or unsubstituted aryl, substituted or unsubstituted 1-20 carbon atom, preferably 1-17 carbon The alkyl and 3-20 carbon atom of sub, more preferable 1-14 carbon atom, preferably 5-8 carbon atom naphthenic base in it is any one Kind.

Wherein, the naphthenic base of the substituted or unsubstituted aryl, the alkyl of 1-20 carbon atom and 3-20 carbon atom It is same as described above.

Substituent group in the alkyl of the 1-20 substituted carbon atom can be halogen or aryl.The aryl with it is above-mentioned It is identical.

It is describedSuch as can beWithIn Any one.

- the CR₅R₆It such as can be-CH₂-、WithIn any one.

- the NR₇Such as can for-NH-, WithIn any one.Wherein, Ph indicates phenyl, Me indicates that methyl, Et indicate that ethyl, Pr indicate that n-propyl, Bu indicate normal-butyl.

In Formula V and V', Y is-NR₇, any one in-O- and-S-.Wherein ,-the NR₇It is same as described above.

In Formulas I-VI, Z^-It can be Cl^-、Br^-、I^-、BF₄ ^-、CF₃SO₃ ^-、CH₃COO^-、(CF₃SO₂)₂N^-、NO₃ ^-、ClO₄ ^-、PF₆ ^- And BPh₄ ^-In any one.

In accordance with the present invention it is preferred that in the metal bridge location fused ring compound,

A is any one in H, F, Cl, Br and SCN.

L is at least one of CO ligand, triphenylphosphine ligand, trimethyl-phosphine ligand, triethyl phosphine ligand.

In formula III and III', X is-O- ,-S- ,-CH₂-、 WithIn any one.

In Formula V and V', Y is any one in-O- ,-S- and-NPh-.

In Formulas I-VI, Z^-For Cl^-、Br^-、BF₄ ^-、CF₃SO₃ ^-、PF₆ ^-And BPh₄ ^-In any one.

R₁ ⁺The cationic substituent on position to indicate number 2 or 5 on Formulas I-VI, and R₁ ⁺For triphenylphosphine sun It is any one in ion, trimethyl-phosphine cation, triethyl phosphine cation, Trimethylamine cation and triethylamine cation Kind.

R₂On at least one of position to indicate number 1,4,5,6,8 and 9 on Formulas I-VI, and and R₁ ⁺Institute is in place Set different substituent groups.

R₃The substituent group at least one of position to indicate number 1,4,5,6,8 and 9 on Formulas I '-VI'.

R₂And R₃Respectively independently selected from-H ,-F ,-Cl ,-Br ,-SCN ,-CN ,-OPh ,-SPh, (-CONMe₂) andIn any one.

The position 2,3- or 4 in Formulas I-VI and I'-VI' has cyclic substituents, and the cyclic substituents at the position 5- ForWithIn any one.

According to the present invention, it is further preferred that the metal bridge location fused ring compound is any one in following compound Kind:

In the above compound, [Ru]¹For RuA (PPh₃)₂, [Ru]²For RuCO (PPh₃)₂, [Ru]³For Ru (PPh₃)₂, [Ru]⁴ For RuA₂PPh₃, [Rh]¹For Rh (PPh₃)₂, [Rh]²For RhA (PPh₃)₂, [Rh]³For RhAPPh₃, [Rh]⁴For RhAPPh₃, [Ir]¹ For Ir (PPh₃)₂, [Ir]²For IrA (PPh₃)₂, [Ir]³For IrAPPh₃, [Ir]⁴For IrAPPh₃；Wherein, A H, Cl or SCN.

Wherein, Me is methyl, and Ph is phenyl,For triphenylphosphine cation, Et is ethyl, BF₄ ^-For tetrafluoro boric acid yin Ion, CF₃SO₃ ^-For trifluoromethanesulfonic acid anion.

According to the second aspect of the invention, the present invention provides the preparation methods of the miscellaneous fused ring compound of above-mentioned metal, should Method includes:

Using Formula VII compound represented and ruthenium complex by cycloaddition reaction preparation as [M]¹For RuAL₂When Formulas I institute The compound shown；Preparation is reacted in organic solvent as [M] with alkali 1 using Formula II compound represented¹For RhL₂Or IrL₂Up-to-date style I compound represented.

In one embodiment, in the preparation method of Formulas I compound represented, as [M]¹For RuAL₂When, preparation Process includes: that Formula VII compound represented and ruthenium complex are carried out cycloaddition reaction.

In one embodiment, in the preparation method of Formulas I compound represented, as [M]¹For RhL₂When, it prepared Journey includes: to be reacted in organic solvent using Formula II compound represented with alkali 1；Wherein, in Formula II, [M]²For RhAL₂.As [M ]²For RhAL₂When, the preparation process of Formula II compound represented includes: that Formula VII compound represented and rhodium complex are carried out ring Addition reaction.

In one embodiment, in the preparation method of Formulas I compound represented, as [M]¹For IrL₂When, it prepared Journey includes: to be reacted in organic solvent using Formula II compound represented with alkali 1；Wherein, in Formula II, [M]²For IrAL₂.As [M ]²For IrAL₂When, the preparation process of Formula II compound represented includes: that Formula VII compound represented and complex of iridium are carried out ring Addition reaction.

[M] is worked as by cycloaddition reaction preparation with rhodium complex and complex of iridium respectively using Formula VII compound represented² For RhAL₂Or IrAL₂When Formula II compound represented；Add alternatively, nucleophilic occurs with nucleopilic reagent using Formulas I compound represented At reaction preparation formula II compound represented.

In one embodiment, in the preparation method of Formula II compound represented, as [M]²For RuL₃When, preparation Process includes: that nucleophilic addition occurs using Formulas I compound represented and nucleopilic reagent；Wherein, in Formulas I, [M]¹For RuAL₂。 As [M]¹For RuAL₂When, the preparation process of Formulas I compound represented include: by Formula VII compound represented and ruthenium complex into Row cycloaddition reaction.

In one embodiment, in the preparation method of Formula II compound represented, as [M]²For RhAL₂When, preparation Process includes: that Formula VII compound represented and rhodium complex are carried out cycloaddition reaction.

In one embodiment, in the preparation method of Formula II compound represented, as [M]²For IrAL₂When, preparation Process includes: that Formula VII compound represented and complex of iridium are carried out cycloaddition reaction.

Using Formulas I compound represented withNucleophilic addition preparation occurs when X isUp-to-date style III compound represented；Pass through ring with ruthenium complex, rhodium complex and complex of iridium respectively using Formula VIII compound represented Addition reaction preparation is-CR as X₅R₆When formula III compound represented；It is reacted using Formulas I compound represented with water or oxygen Preparation formula III compound represented when X is-O-；Use Formulas I compound represented and H₂S, at least one of NaHS and S Reaction preparation formula III compound represented when X is-S-；When to react with Se preparation X using Formulas I compound represented be-Se- Formula III compound represented；Use Formulas I compound represented and R₇NH₂Reaction preparation X is-NR₇When formula III shown in Compound.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For RuAL₂And X isWhen, preparation process include: by Formulas I compound represented withNucleophilic addition occurs；Wherein, In Formulas I, [M]¹For RuAL₂.As [M]¹For RuAL₂When, the preparation process of Formulas I compound represented includes: will be shown in Formula VII Compound and ruthenium complex carry out cycloaddition reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For RuAL₂And X be- CR₅R₆When, preparation process includes: that cycloaddition reaction is occurred for Formula VIII compound represented and ruthenium complex.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For RuAL₂And X be- When O-, preparation process includes: to be reacted using Formulas I compound represented with water or oxygen；Wherein, in Formulas I, [M]¹For RuAL₂。 As [M]¹For RuAL₂When, the preparation process of Formulas I compound represented include: by Formula VII compound represented and ruthenium complex into Row cycloaddition reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For RuAL₂And X be- When S-, preparation process includes: using Formulas I compound represented and H₂S, at least one of NaHS and S react；Wherein, Formulas I In, [M]¹For RuAL₂.As [M]¹For RuAL₂When, the preparation process of Formulas I compound represented includes: by chemical combination shown in Formula VII Object and ruthenium complex carry out cycloaddition reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For RuAL₂And X be- When Se-, preparation process includes: to be reacted using Formulas I compound represented with Se；Wherein, in Formulas I, [M]¹For RuAL₂.As [M]¹ For RuAL₂When, the preparation process of Formulas I compound represented includes: that Formula VII compound represented is carried out ring with ruthenium complex to add At reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For RuAL₂And X be- NR₇When, preparation process includes: using Formulas I compound represented and R₇NH₂Reaction；Wherein, in Formulas I, [M]¹For RuAL₂.When [M]¹For RuAL₂When, the preparation process of Formulas I compound represented includes: to carry out Formula VII compound represented and ruthenium complex Cycloaddition reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For RhL₂And X isWhen, preparation process include: by Formulas I compound represented withNucleophilic addition occurs；Wherein, In Formulas I, [M]¹For RhL₂.As [M]¹For RhL₂When, the preparation process of Formulas I compound represented includes: by chemical combination shown in Formula II Object reacts in organic solvent with alkali 1；Wherein, in Formula II, [M]²For RhAL₂.As [M]²For RhAL₂When, chemical combination shown in Formula II The preparation process of object includes: that Formula VII compound represented and rhodium complex are carried out cycloaddition reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For RhL₂And X be- CR₅R₆When, preparation process includes: that cycloaddition reaction is occurred for Formula VIII compound represented and rhodium complex.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For RhL₂And X is-O- When, preparation process includes: to be reacted using Formulas I compound represented with water or oxygen；Wherein, in Formulas I, [M]¹For RhL₂.When [M]¹For RhL₂When, the preparation process of Formulas I compound represented include: by Formula II compound represented and alkali 1 in organic solvent Reaction；Wherein, in Formula II, [M]²For RhAL₂.As [M]²For RhAL₂When, the preparation process of Formula II compound represented include: by Formula VII compound represented and rhodium complex carry out cycloaddition reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For RhL₂And X is-S- When, preparation process includes: using Formulas I compound represented and H₂S, at least one of NaHS and S react；Wherein, Formulas I In, [M]¹For RhL₂.As [M]¹For RhL₂When, the preparation process of Formulas I compound represented includes: by Formula II compound represented It is reacted in organic solvent with alkali 1；Wherein, in Formula II, [M]²For RhAL₂.As [M]²For RhAL₂When, Formula II compound represented Preparation process include: that Formula VII compound represented and rhodium complex are subjected to cycloaddition reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For RhL₂And X be- When Se-, preparation process includes: to be reacted using Formulas I compound represented with Se；Wherein, in Formulas I, [M]¹For RhL₂.As [M]¹ For RhL₂When, the preparation process of Formulas I compound represented includes: that Formula II compound represented and alkali 1 is anti-in organic solvent It answers；Wherein, in Formula II, [M]²For RhAL₂.As [M]²For RhAL₂When, the preparation process of Formula II compound represented includes: by formula VII compound represented and rhodium complex carry out cycloaddition reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For RhL₂And X be- NR₇When, preparation process includes: using Formulas I compound represented and R₇NH₂Reaction；Wherein, in Formulas I, [M]¹For RhL₂.When [M]¹For RhL₂When, the preparation process of Formulas I compound represented include: by Formula II compound represented and alkali 1 in organic solvent Reaction；Wherein, in Formula II, [M]²For RhAL₂.As [M]²For RhAL₂When, the preparation process of Formula II compound represented include: by Formula VII compound represented and rhodium complex carry out cycloaddition reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For IrL₂And X isWhen, preparation process include: by Formulas I compound represented withNucleophilic addition occurs；Wherein, In Formulas I, [M]¹For IrL₂.As [M]¹For IrL₂When, the preparation process of Formulas I compound represented includes: by chemical combination shown in Formula II Object reacts in organic solvent with alkali 1；Wherein, in Formula II, [M]²For IrAL₂.As [M]²For IrAL₂When, chemical combination shown in Formula II The preparation process of object includes: that Formula VII compound represented and complex of iridium are carried out cycloaddition reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For IrL₂And X be- CR₅R₆When, preparation process includes: that cycloaddition reaction is occurred for Formula VIII compound represented and complex of iridium.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For IrL₂And X is-O- When, preparation process includes: to be reacted using Formulas I compound represented with water or oxygen；Wherein, in Formulas I, [M]¹For IrL₂.When [M]¹For IrL₂When, the preparation process of Formulas I compound represented include: by Formula II compound represented and alkali 1 in organic solvent Reaction；Wherein, in Formula II, [M]²For IrAL₂.As [M]²For IrAL₂When, the preparation process of Formula II compound represented include: by Formula VII compound represented and complex of iridium carry out cycloaddition reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For IrL₂And X is-S- When, preparation process includes: using Formulas I compound represented and H₂S, at least one of NaHS and S react；Wherein, Formulas I In, [M]¹For IrL₂.As [M]¹For IrL₂When, the preparation process of Formulas I compound represented includes: by Formula II compound represented It is reacted in organic solvent with alkali 1；Wherein, in Formula II, [M]²For IrAL₂.As [M]²For IrAL₂When, Formula II compound represented Preparation process include: that Formula VII compound represented and complex of iridium are subjected to cycloaddition reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For IrL₂And X be- When Se-, preparation process includes: to be reacted using Formulas I compound represented with Se；Wherein, in Formulas I, [M]¹For IrL₂.As [M]¹ For IrL₂When, the preparation process of Formulas I compound represented includes: that Formula II compound represented and alkali 1 is anti-in organic solvent It answers；Wherein, in Formula II, [M]²For IrAL₂.As [M]²For IrAL₂When, the preparation process of Formula II compound represented includes: by formula VII compound represented and complex of iridium carry out cycloaddition reaction.

In one embodiment, in the preparation method of formula III compound represented, as [M]¹For IrL₂And X be- NR₇When, preparation process includes: using Formulas I compound represented and R₇NH₂Reaction；Wherein, in Formulas I, [M]¹For IrL₂.When [M]¹For IrL₂When, the preparation process of Formulas I compound represented include: by Formula II compound represented and alkali 1 in organic solvent Reaction；Wherein, in Formula II, [M]²For IrAL₂.As [M]²For IrAL₂When, the preparation process of Formula II compound represented include: by Formula VII compound represented and complex of iridium carry out cycloaddition reaction.

Pass through chemical combination shown in cycloaddition reaction preparation formula IV using Formula X compound represented and Formulas I compound represented Object.

In one embodiment, in the preparation method of formula IV compound represented, as [M]¹For RuAL₂When, preparation Process includes: that Formula X compound represented and Formulas I compound represented are carried out cycloaddition reaction；Wherein, in Formulas I, [M]¹For RuAL₂.As [M]¹For RuAL₂When, the preparation process of Formulas I compound represented includes: to match Formula VII compound represented with ruthenium It closes object and carries out cycloaddition reaction.

In one embodiment, in the preparation method of formula IV compound represented, as [M]¹For RhL₂When, preparation Process includes: that Formula X compound represented and Formulas I compound represented are carried out cycloaddition reaction；Wherein, in Formulas I, [M]¹For RhL₂.As [M]¹For RhL₂When, the preparation process of Formulas I compound represented includes: to have Formula II compound represented and alkali 1 It is reacted in solvent；Wherein, in Formula II, [M]²For RhAL₂.As [M]²For RhAL₂When, the preparation of Formula II compound represented Journey includes: that Formula VII compound represented and rhodium complex are carried out cycloaddition reaction.

In one embodiment, in the preparation method of formula IV compound represented, as [M]¹For IrL₂When, preparation Process includes: that Formula X compound represented and Formulas I compound represented are carried out cycloaddition reaction；Wherein, in Formulas I, [M]¹For IrL₂.As [M]¹For IrL₂When, the preparation process of Formulas I compound represented includes: to have Formula II compound represented and alkali 1 It is reacted in solvent；Wherein, in Formula II, [M]²For IrAL₂.As [M]²For IrAL₂When, the preparation of Formula II compound represented Journey includes: that Formula VII compound represented and complex of iridium are carried out cycloaddition reaction.

Pass through chemical combination shown in ring expansion preparation formula V using Formula XI compound represented and formula III compound represented Object.

In one embodiment, in the preparation method of Formula V compound represented, as [M]³For RuL₂When, it prepared Journey includes: that Formula XI compound represented and formula III compound represented are carried out ring expansion；Wherein, in formula III, [M]¹For RuAL₂.As [M]¹For RuAL₂When, the preparation method of formula III compound represented is as described above.

In one embodiment, in the preparation method of Formula V compound represented, as [M]³When for RhAL, preparation Process includes: that Formula XI compound represented and formula III compound represented are carried out ring expansion；Wherein, in formula III, [M]¹ For RhL₂.As [M]¹For RhL₂When, the preparation method of formula III compound represented is as described above.

In one embodiment, in the preparation method of Formula V compound represented, as [M]³When for IrAL, preparation Process includes: that Formula XI compound represented and formula III compound represented are carried out ring expansion；Wherein, in formula III, [M]¹ For IrL₂.As [M]¹For IrL₂When, the preparation method of formula III compound represented is as described above.

Pass through cycloaddition reaction system with ruthenium complex, rhodium complex and complex of iridium respectively using Formula IX compound represented Standby Formula IV compound represented.

In one embodiment, in the preparation method of Formula IV compound represented, as [M]⁴For RuA₂When L, preparation Process includes: that Formula IX compound represented and ruthenium complex are carried out cycloaddition reaction.

In one embodiment, in the preparation method of Formula IV compound represented, as [M]⁴When for RhAL, preparation Process includes: that Formula IX compound represented and rhodium complex are carried out cycloaddition reaction.

In one embodiment, in the preparation method of Formula IV compound represented, as [M]⁴When for IrAL, preparation Process includes: that Formula IX compound represented and complex of iridium are carried out cycloaddition reaction.

In one embodiment, in the preparation method of Formulas I ' compound represented, as [M]¹For RuAL₂When, preparation Process includes: to hydrolyze Formulas I compound represented in the aqueous solution of alkali 2；Wherein, in Formulas I, [M]¹For RuAL₂.As [M]¹For RuAL₂When, the preparation method of Formulas I compound represented is as described above.

In one embodiment, in the preparation method of Formulas I ' compound represented, as [M]¹For RhL₂When, preparation Process includes: to hydrolyze Formulas I compound represented in the aqueous solution of alkali 2；Wherein, in Formulas I, [M]¹For RhL₂.As [M]¹For RhL₂When, the preparation method of Formulas I compound represented is as described above.

In one embodiment, in the preparation method of Formulas I ' compound represented, as [M]¹For IrL₂When, preparation Process includes: to hydrolyze Formulas I compound represented in the aqueous solution of alkali 2；Wherein, in Formulas I, [M]¹For IrL₂.As [M]¹For IrL₂When, the preparation method of Formulas I compound represented is as described above.

Nucleophilic addition preparation formula II' compound represented occurs using Formulas I ' compound represented and nucleopilic reagent； Carry out preparation formula II' compound represented alternatively, hydrolyzing in the aqueous solution of alkali 2 using Formula II compound represented.

In one embodiment, in the preparation method of Formula II ' compound represented, as [M]²For RuL₃When, preparation Process includes: that nucleophilic addition is occurred for Formulas I ' compound represented and nucleopilic reagent；Wherein, Formulas I ' in, [M]¹For RuAL₂。 As [M]¹For RuAL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of Formula II ' compound represented, as [M]²For RuL₃When, preparation Process includes: to hydrolyze Formula II compound represented in the aqueous solution of alkali 2；Wherein, in Formula II, [M]²For RuL₃.As [M]²For RuL₃When, the preparation method of Formula II compound represented is as described above.

In one embodiment, in the preparation method of Formula II ' compound represented, as [M]²For RhAL₂When, system Standby process includes: that nucleophilic addition is occurred for Formulas I ' compound represented and nucleopilic reagent；Wherein, Formulas I ' in, [M]¹For RhL₂.As [M]¹For RhL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of Formula II ' compound represented, as [M]²For RhAL₂When, system Standby process includes: to hydrolyze Formula II compound represented in the aqueous solution of alkali 2；Wherein, in Formula II, [M]²For RhAL₂.As [M ]²For RuL₃When, the preparation method of Formula II compound represented is as described above.

In one embodiment, in the preparation method of Formula II ' compound represented, as [M]²For IrAL₂When, system Standby process includes: that nucleophilic addition is occurred for Formulas I ' compound represented and nucleopilic reagent；Wherein, Formulas I ' in, [M]¹For IrL₂.As [M]¹For IrL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of Formula II ' compound represented, as [M]²For IrAL₂When, system Standby process includes: to hydrolyze Formula II compound represented in the aqueous solution of alkali 2；Wherein, in Formula II, [M]²For IrAL₂.As [M ]²For IrAL₂When, the preparation method of Formula II compound represented is as described above.

Using Formulas I ' compound represented withNucleophilic addition preparation occurs when X isUp-to-date style III' compound represented；Preparation is reacted when X is shown in-O- up-to-date style III' with water or oxygen using Formulas I ' compound represented Compound；Use Formulas I ' compound represented and H₂S, NaHS and S₈At least one of reaction preparation when X be-S- up-to-date style III' Compound represented；Preparation is reacted when X is-Se- up-to-date style III' compound represented with Se using Formulas I ' compound represented；Make With Formulas I ' compound represented and R₇NH₂Reaction preparation X is-NR₇When formula III ' compound represented；Alternatively, using formula III Compound represented hydrolyzes in the aqueous solution of alkali 2 carrys out preparation formula III' compound represented.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RuAL₂And X isWhen, preparation process include: by Formulas I ' compound represented withNucleophilic addition occurs；Wherein, Formulas I ' in, [M]¹For RuAL₂.As [M]¹For RuAL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RuAL₂And X isWhen, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, formula III In, [M]¹For RuAL₂And X isAs [M]¹For RuAL₂And X isWhen, formula III compound represented Preparation method it is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RuAL₂And X be- CR₅R₆When, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹For RuAL₂And X is-CR₅R₆-.As [M]¹For RuAL₂And X is-CR₅R₆When, the preparation side of formula III compound represented Method is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RuAL₂And X be- When O-, preparation process includes: to be reacted using Formulas I ' compound represented with water or oxygen；Wherein, Formulas I ' in, [M]¹For RuAL₂.As [M]¹For RuAL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RuAL₂And X be- When O-, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹ For RuAL₂And X is-O-.As [M]¹For RuAL₂And X be-O- when, the preparation method of formula III compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RuAL₂And X be- When S-, preparation process includes: using Formulas I ' compound represented and H₂S, at least one of NaHS and S react；Wherein, formula In I', [M]¹For RuAL₂.As [M]¹For RuAL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RuAL₂And X be- When S-, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹ For RuAL₂And X is-S-.As [M]¹For RuAL₂And X be-S- when, the preparation method of formula III compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RuAL₂And X be- When Se-, preparation process includes: to be reacted using Formulas I ' compound represented with Se；Wherein, Formulas I ' in, [M]¹For RuAL₂.When [M]¹For RuAL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RuAL₂And X be- When Se-, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹ For RuAL₂And X is-Se-.As [M]¹For RuAL₂And X be-Se- when, the preparation method of formula III compound represented institute as above It states.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RuAL₂And X be- NR₇When, preparation process includes: by Formulas I ' compound represented and R₇NH₂Reaction；Wherein, Formulas I ' in, [M]¹For RuAL₂.When [M]¹For RuAL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RuAL₂And X be- NR₇When, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹ For RuAL₂And X is-NR₇-.As [M]¹For RuAL₂And X is-NR₇When, the preparation method of formula III compound represented institute as above It states.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RhL₂And X isWhen, preparation process include: by Formulas I ' compound represented withNucleophilic addition occurs；Its In, Formulas I ' in, [M]¹For RhL₂.As [M]¹For RhL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RhL₂And X isWhen, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, formula III In, [M]¹For RhL₂And X isAs [M]¹For RhL₂And X isWhen, formula III compound represented Preparation method is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RhL₂And X be- CR₅R₆When, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹For RhL₂And X is-CR₅R₆-.As [M]¹For RhL₂And X is-CR₅R₆When, the preparation method of formula III compound represented As described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RhL₂And X be- When O-, preparation process includes: to be reacted using Formulas I ' compound represented with water or oxygen；Wherein, Formulas I ' in, [M]¹For RhL₂。 As [M]¹For RhL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RhL₂And X be- When O-, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹ For RhL₂And X is-O-.As [M]¹For RhL₂And X be-O- when, the preparation method of formula III compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RhL₂And X be- When S-, preparation process includes: using Formulas I ' compound represented and H₂S, at least one of NaHS and S react；Wherein, formula In I', [M]¹For RhL₂.As [M]¹For RhL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RhL₂And X be- When S-, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹ For RhL₂And X is-S-.As [M]¹For RhL₂And X be-S- when, the preparation method of formula III compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RhL₂And X be- When Se-, preparation process includes: to be reacted using Formulas I ' compound represented with Se；Wherein, Formulas I ' in, [M]¹For RhL₂.As [M ]¹For RhL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RhL₂And X be- When Se-, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹ For RhL₂And X is-Se-.As [M]¹For RhL₂And X be-Se- when, the preparation method of formula III compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RhL₂And X be- NR₇When, preparation process includes: by Formulas I ' compound represented and R₇NH₂Reaction；Wherein, Formulas I ' in, [M]¹For RhL₂.When [M]¹For RhL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For RhL₂And X be- NR₇When, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹ For RhL₂And X is-NR₇-.As [M]¹For RhL₂And X is-NR₇When, the preparation method of formula III compound represented institute as above It states.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For IrL₂And X isWhen, preparation process include: by Formulas I ' compound represented withNucleophilic addition occurs；Its In, Formulas I ' in, [M]¹For IrL₂.As [M]¹For IrL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For IrL₂And X isWhen, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, formula III In, [M]¹For IrL₂And X isAs [M]¹For IrL₂And X isWhen, formula III compound represented Preparation method is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For IrL₂And X be- CR₅R₆When, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹For IrL₂And X is-CR₅R₆-.As [M]¹For IrL₂And X is-CR₅R₆When, the preparation method of formula III compound represented As described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For IrL₂And X be- When O-, preparation process includes: to be reacted using Formulas I ' compound represented with water or oxygen；Wherein, Formulas I ' in, [M]¹For IrL₂。 As [M]¹For IrL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For IrL₂And X be- When O-, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹ For IrL₂And X is-O-.As [M]¹For IrL₂And X be-O- when, the preparation method of formula III compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For IrL₂And X be- When S-, preparation process includes: using Formulas I ' compound represented and H₂S, at least one of NaHS and S react；Wherein, formula In I', [M]¹For IrL₂.As [M]¹For IrL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For IrL₂And X be- When S-, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹ For IrL₂And X is-S-.As [M]¹For IrL₂And X be-S- when, the preparation method of formula III compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For IrL₂And X be- When Se-, preparation process includes: to be reacted using Formulas I ' compound represented with Se；Wherein, Formulas I ' in, [M]¹For IrL₂.As [M ]¹For IrL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For IrL₂And X be- When Se-, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹ For IrL₂And X is-Se-.As [M]¹For IrL₂And X be-Se- when, the preparation method of formula III compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For IrL₂And X be- NR₇When, preparation process includes: by Formulas I ' compound represented and R₇NH₂Reaction；Wherein, Formulas I ' in, [M]¹For IrL₂.When [M]¹For IrL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula III ' compound represented, as [M]¹For IrL₂And X be- NR₇When, preparation process includes: to hydrolyze formula III compound represented in the aqueous solution of alkali 2；Wherein, in formula III, [M]¹ For IrL₂And X is-NR₇-.As [M]¹For IrL₂And X is-NR₇When, the preparation method of formula III compound represented institute as above It states.

Using Formula X compound represented and Formulas I ' compound represented by changing shown in cycloaddition reaction preparation formula IV' Close object；Or it is hydrolyzed in the aqueous solution of alkali 2 using formula IV compound represented and carrys out preparation formula IV' compound represented.

In one embodiment, in the preparation method of formula IV ' compound represented, as [M]¹For RuAL₂When, system Standby process includes: that Formula X compound represented and Formulas I ' compound represented are carried out cycloaddition reaction；Wherein, Formulas I ' in, [M]¹ For RuAL₂.As [M]¹For RuAL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula IV ' compound represented, as [M]¹For RuAL₂When, system Standby process includes: to hydrolyze formula IV compound represented in the aqueous solution of alkali 2；Wherein, in formula IV, [M]¹For RuAL₂.As [M ]¹For RuAL₂When, the preparation method of formula IV compound represented is as described above.

In one embodiment, in the preparation method of formula IV ' compound represented, as [M]¹For RhL₂When, preparation Process includes: that Formula X compound represented and Formulas I ' compound represented are carried out cycloaddition reaction；Wherein, Formulas I ' in, [M]¹For RhL₂.As [M]¹For RhL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula IV ' compound represented, as [M]¹For RhL₂When, preparation Process includes: to hydrolyze formula IV compound represented in the aqueous solution of alkali 2；Wherein, in formula IV, [M]¹For RhL₂.As [M]¹For RhL₂When, the preparation method of formula IV compound represented is as described above.

In one embodiment, in the preparation method of formula IV ' compound represented, as [M]¹For IrL₂When, preparation Process includes: that Formula X compound represented and Formulas I ' compound represented are carried out cycloaddition reaction；Wherein, Formulas I ' in, [M]¹For IrL₂.As [M]¹For IrL₂When, the preparation method of Formulas I ' compound represented is as described above.

In one embodiment, in the preparation method of formula IV ' compound represented, as [M]¹For IrL₂When, preparation Process includes: to hydrolyze formula IV compound represented in the aqueous solution of alkali 2；Wherein, in formula IV, [M]¹For IrL₂.As [M]¹For IrL₂When, the preparation method of formula IV compound represented is as described above.

Using Formula XI compound represented and formula III ' compound represented by changing shown in ring expansion preparation formula V' Close object；Or it is hydrolyzed in the aqueous solution of alkali 2 using Formula V compound represented and carrys out preparation formula V' compound represented.

In one embodiment, in the preparation method of Formula V ' compound represented, as [M]³For RuL₂When, preparation Process includes: that Formula XI compound represented and formula III ' compound represented are carried out ring expansion；Wherein, formula III ' in, [M ]¹For RuAL₂.As [M]¹For RuAL₂When, the preparation method of formula III ' compound represented is as described above.

In one embodiment, in the preparation method of Formula V ' compound represented, as [M]³For RuL₂When, preparation Process includes: to hydrolyze Formula V compound represented in the aqueous solution of alkali 2；Wherein, in Formula V, [M]³For RuL₂.As [M]³For RuL₂When, the preparation method of Formula V compound represented is as described above.

In one embodiment, in the preparation method of Formula V ' compound represented, as [M]³When for RhAL, preparation Process includes: that Formula XI compound represented and formula III ' compound represented are carried out ring expansion；Wherein, formula III ' in, [M ]¹For RhL₂.As [M]¹For RhL₂When, the preparation method of formula III ' compound represented is as described above.

In one embodiment, in the preparation method of Formula V ' compound represented, as [M]³When for RhAL, preparation Process includes: to hydrolyze Formula V compound represented in the aqueous solution of alkali 2；Wherein, in Formula V, [M]³For RhAL.As [M]³For When RhAL, the preparation method of Formula V compound represented is as described above.

In one embodiment, in the preparation method of Formula V ' compound represented, as [M]³When for IrAL, preparation Process includes: that Formula XI compound represented and formula III ' compound represented are carried out ring expansion；Wherein, formula III ' in, [M ]¹For IrL₂.As [M]¹For IrL₂When, the preparation method of formula III ' compound represented is as described above.

In one embodiment, in the preparation method of Formula V ' compound represented, as [M]³When for IrAL, preparation Process includes: to hydrolyze Formula V compound represented in the aqueous solution of alkali 2；Wherein, in Formula V, [M]³For IrAL.As [M]³For When IrAL, the preparation method of Formula V compound represented is as described above.

It is hydrolyzed in the aqueous solution of alkali 2 using Formula IV compound represented and carrys out preparation formula VI' compound represented.

In one embodiment, in the preparation method of Formula IV ' compound represented, as [M]⁴For RuA₂When L, system Standby process includes: to hydrolyze Formula IV compound represented in the aqueous solution of alkali 2；Wherein, in Formula IV, [M]⁴For RuA₂L.As [M ]⁴For RuA₂When L, the preparation method of Formula IV compound represented is as described above.

In one embodiment, in the preparation method of Formula IV ' compound represented, as [M]⁴When for RhAL, system Standby process includes: to hydrolyze Formula IV compound represented in the aqueous solution of alkali 2；Wherein, in Formula IV, [M]⁴For RhAL.As [M]⁴ When for RhAL, the preparation method of Formula IV compound represented is as described above.

In one embodiment, in the preparation method of Formula IV ' compound represented, as [M]⁴When for IrAL, system Standby process includes: to hydrolyze Formula IV compound represented in the aqueous solution of alkali 2；Wherein, in Formula IV, [M]⁴For IrAL.As [M]⁴ When for IrAL, the preparation method of Formula IV compound represented is as described above.

Wherein, in Formula VII-XI,

G is-O- ,-S- ,-CR₁₈R₁₉-、-SiR₂₀R₂₁And-NR₂₂In any one.

Wherein, R₁₈、R₁₉、R₂₀、R₂₁And R₂₂It is separately hydrogen, 1-20 carbon atom, preferably 1-17 carbon atom, more It is preferred that the alkyl of 1-8 carbon atom, 1-20 carbon atom, preferably 1-17 carbon atom, more preferable 1-8 carbon atom ester group, 1-20 carbon atom, preferably 1-17 carbon atom, the acyl group of more preferable 1-8 carbon atom, 3-20 carbon atom, preferably 3-17 Carbon atom, the naphthenic base of more preferable 3-8 carbon atom, 1-20 carbon atom, preferably 1-17 carbon atom, more preferable 1-8 carbon The halogenated alkyl of atom, itrile group, nitro, substituted or unsubstituted aryl andIn any one.Wherein, R₂₃It can be with For any one in the alkyl and substituted or unsubstituted phenyl of 1-8 carbon atom.

The alkyl of the 1-20 carbon atom, the ester group of 1-20 carbon atom, 1-20 carbon atom acyl group, 3-20 carbon The naphthenic base of atom is same as described above.

The halogenated alkyl of the 1-20 carbon atom is that F, Cl, Br or I replace in the alkyl of above-mentioned 1-20 carbon atom At least one hydrogen is formed by substituent group.

R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃、R₁₄、R₁₅、R₁₆And R₁₇The range and R for the substituent group that can be selected₂Or R₃It is identical.

M and n is respectively the integer of 1-6, and m+n < 8.For example, under the premise of m+n < 8, m and n can separately be 1,2,3,4,5 or 6.Specifically, 1 m, n 1,2,3,4,5 or 6；Or m is 2, n 1,2,3,4 or 5；Or m is that 3, n is 1,2,3 or 4；Or m is 4, n 1,2 or 3；Or it is 1 or 2 that m, which is 5, n,；Or m is 6, n 1.

Wherein,

The ruthenium complex can be RuCl₂(PPh₃)₃、RuCl₂(PMe₃)₃、RuCl₂(PEt₃)₃And RuCl₂(PCy₃)₃In At least one.

The rhodium complex can be RhCl (PPh₃)₃、RhHCl₂(PPh₃)₃、RhCl(PMe₃)₃、RhCl(PEt₃)₃With RhCl(PCy₃)₃At least one of.

The complex of iridium can be IrHCl₂(PPh₃)₃、IrCl(PPh₃)₃、IrCl(PMe₃)₃、IrCl(PEt₃)₃With IrCl(PCy₃)₃At least one of.

The alkali 1 can be the carbonate and/or hydride of alkali metal.The alkali 1 for example can be Na₂CO₃、K₂CO₃、 Cs₂CO₃、CaH₂At least one of with NaH.

The alkali 2 can be the hydroxide of alkali metal.The alkali 2 for example can be NaOH and/or KOH.The alkali 2 The concentration of aqueous solution can be 0.01-10 mol/L, preferably 0.5-5 mol/L.

The nucleopilic reagent can be halogen simple substance, alcohol, sodium alkoxide, potassium alcoholate, mercaptan, sodium mercaptides, the sulphur of 1-10 carbon atom At least one of potassium alcoholate, phenol, phenol sodium and phenol potassium.Preferably, the nucleopilic reagent is Cl₂、Br₂, sodium methoxide, sodium ethoxide, phenol Sodium, p-cresol sodium, benzenethiol sodium, toluene-ω-thiol sodium and at least one of methoxybenzenethiol sodium.

It is describedSuch as can beWithIn It is at least one.

Wherein, in method of the present invention,

The reaction condition of the cycloaddition reaction may include that reaction temperature is -100-200 DEG C, preferably 0-60 DEG C；Reaction Time is -2 days 1 minute, preferably -1 day 0.5 hour.

The reaction condition of the nucleophilic addition may include that reaction temperature is -100-200 DEG C, preferably 0-60 DEG C；Instead It is -2 days 1 minute, preferably -1 day 0.5 hour between seasonable.

The reaction condition of the ring expansion may include that reaction temperature is -100-200 DEG C, preferably 0-60 DEG C；When reaction Between be -2 days 1 minute, preferably -1 day 0.5 hour.

Method according to the present invention, all reactions can carry out in the presence of an organic.Preferably, The organic solvent be methylene chloride, dichloroethanes, chloroform, methanol, ethyl alcohol, acetone, butanone, tetrahydrofuran, dimethyl sulfoxide, At least one of N,N-dimethylformamide, toluene, benzene, dioxane, ether and acetonitrile.

Method according to the present invention, it is described after the reaction was completed, mixture after the reaction of acquisition can be concentrated, Solid matter is obtained after precipitating, then the solid matter of acquisition is filtered, washed and obtains the metal after pillar layer separation Bridge location fused ring compound.

Wherein, the Formula VII, Formula VIII and Formula IX compound represented the preparation method is as follows:

Work as R₁₀When for hydrogen, this method comprises:

By Formula XII compound represented and organometallic reagent RM₁And/or RM₂Z carries out metal in non-protonic solvent Exchange reaction, and by obtained reaction mixture and Formula XIII compound represented haptoreaction, obtain J base shown in Formula XIV The chain polyyne compound of group's protection；The chain polyyne compound of J radical protection shown in Formula XIV is subjected to deprotection group again It handles, chain polyyne compound shown in acquisition Formula VII, Formula VIII and Formula IX:

Wherein,

In Formula XIII, J is the blocking group for protecting alkynyl.J can be TMS (trimethyl silicon substrate), TES (triethyl group Silicon substrate) and TIPS (triisopropylsilyl) in any one.

In Formula XIII and XIV, G, m and n are same as described above.

In VII, Formula VIII and Formula IX, R₃₃For-C ≡ C-R₈、Or-C ≡ C-C ≡ C-R₁₃。

The organometallic reagent RM₁Or RM₂R in Z can be alkyl, phenyl and the-NR of 1-8 carbon atom₃₅R₃₆In Any one.Wherein ,-NR₃₅R₃₆In R₃₅And R₃₆It can separately be the alkyl and trimethyl of hydrogen, 1-8 carbon atom Any one in silicon substrate.The alkyl of the 1-8 carbon atom is same as described above.

M₁It can be lithium, sodium or potassium.M₂It can be magnesium.Z can be chlorine, bromine or iodine.

Preferably, RM₁For lithium methide, ethyl-lithium, n-BuLi, tert-butyl lithium, phenyl lithium, lithium diisopropyl amido and double At least one of (trimethyl silicon substrate) amido lithium.

Preferably, RM₂Z is at least one in methyl-magnesium-bromide, ethylmagnesium bromide, methyl-magnesium-chloride and ethylmagnesium chloride Kind.

The chain polyyne compound that J radical protection shown in Formula XIV of the deprotection agent to acquisition can be used carries out remove-insurance Protect group processing.The deprotection agent can be K₂CO₃、Na₂CO₃、Cs₂CO₃、KF、(n-Bu)₄NF (tetra-n-butyl ammonium fluoride), (Et)₄NF (tetraethyl ammonium fluoride), (Me)₄NF (Methanaminium, N,N,N-trimethyl-, fluoride) and (n-Pr)₄In NF (four n-propyl ammonium fluorides) at least It is a kind of.

Preferably, deprotection group is carried out in the chain polyyne compound to J radical protection shown in Formula XIV handle it Before, behaviour is quenched and purified to the mixture of the chain polyyne compound containing J radical protection shown in Formula XIV of acquisition Make.Wherein, quencher used in the quenching operation can be saturated ammonium chloride and/or water.The purification operations can wrap It includes and is extracted using mixture of the organic solvent to the chain polyyne compound containing J radical protection shown in Formula XIV of acquisition It takes, filtering after the organic phase that extraction is obtained is dry, concentration, chromatography obtain chemical combination shown in Formula VII, Formula VIII and Formula IX Object.Wherein, the organic solvent can be ether, n-hexane, toluene, glycol dimethyl ether, Isosorbide-5-Nitrae-dioxane, methylene chloride At least one of with chloroform；The dry operation of the organic phase that described pair of extraction obtains may include using anhydrous magnesium sulfate And/or anhydrous sodium sulfate；The operation of the chromatography may include using silica gel column chromatography and/or neutral alumina.

Preferably, after the chain polyyne compound to J radical protection shown in Formula XIV carries out deprotection group processing The mixture containing chain polyyne compound shown in Formula VII, Formula VIII and Formula IX obtained is quenched and purification operations.Institute State be quenched it is same as above with the method for purification operations.

Work as R₁₀When not being hydrogen, the Formula VII, Formula VIII and Formula IX compound represented the preparation method is as follows:

By Formula XII compound represented and organometallic reagent RM₁And/or RM₂Z carries out metal in non-protonic solvent Exchange reaction, and by obtained reaction mixture and Formula XV compound represented haptoreaction, obtain Formula VII, Formula VIII or formula IX compound represented:

Wherein, organometallic reagent RM₁Or RM₂Z is same as described above.G,R₃₃、R₃₄, m and n it is same as described above.

In the method, to the Formula XII compound represented and organometallic reagent RM₁And/or RM₂The summation of Z Usage ratio is not particularly limited.Preferably, the Formula XII compound represented and organometallic reagent RM₁And/or RM₂Z's The molar ratio of summation is 1:(0.5-1), preferably 1:(0.9-1).When containing RM simultaneously₁And RM₂When Z, to the organometallic reagent RM₁And RM₂The usage ratio of Z is not particularly limited, and the two can be used in mixed way with any molar ratio.

In the method, the non-protonic solvent is not particularly limited.Preferably, the non-protonic solvent is Benzene, toluene, n-hexane, ether, glycol dimethyl ether, tetrahydrofuran and 1,4- dioxane, petroleum ether, at least one in gasoline Kind.

In the method, the Formula XII compound represented and organometallic reagent RM₁And/or RM₂Z can be in inertia Metal exchange reaction is carried out under gas shield.The inert gas does not react to be any with catalyst, raw material and product, and right Reaction does not generate the gas of any negative effect.The inert gas can be at least one in nitrogen, helium, argon gas and neon Kind.The Formula XII compound represented and organometallic reagent RM₁And/or RM₂The condition packet that Z is contacted in non-protonic solvent Including temperature can be -100-30 DEG C, and preferably -78-0 DEG C, the time can be 0.5-10h, preferably 1-3h.

In the method, by Formula XII compound represented and organometallic reagent RM₁And/or RM₂Z is molten in aprotic The reaction mixture that metal exchange reaction obtains is carried out in agent to connect with Formula XIII compound represented or Formula XV compound represented The condition of touching reaction includes that temperature can be -100-30 DEG C, and preferably -78-0 DEG C, the time can be 0.5-10h, preferably 1-5h.

The application according to the third aspect of the present invention, it is preferable that change shown in the Formulas I, I', II, II' and VI It closes object and is particularly suitable for area of solar cell；Formula II compound represented is particularly suitable for lithium-air battery field；Formula III, IV, V, III', IV', V' and VI' compound represented are particularly suitable for photodynamic therapy field.

The application according to the third aspect of the present invention, it is preferable that

In Formulas I compound represented, R₂To indicate the substituent group on digital 1-6, R₂Preferably H；The 2 of digital 1-6 are indicated, The position 3-, the position 3,4-, the position 4,5- and 5, any one in the position 6- are substituted or unsubstituted at the position preferably 4,5- Cyclic substituents；The cyclic substituents are preferably the five-membered ring or hexa-atomic ring substituents being all made of carbon atom, Huo Zheyou The five-membered ring or hexa-atomic ring substituents that any one and carbon atom in oxygen, nitrogen and silicon atom form together；The substituted ring When substituent group on shape substituent group is preferably the ester group of 1-20 carbon atom, Formulas I compound represented is particularly suitable for solar energy Field of batteries further can be used as the photosensitizer of solar battery.

In Formula II compound represented, R₂To indicate the substituent group on digital 1-6, R₂Preferably H；The 2 of digital 1-6 are indicated, The position 3-, the position 3,4-, the position 4,5- and 5, any one in the position 6- are substituted or unsubstituted at the position preferably 4,5- Cyclic substituents；The cyclic substituents are preferably the five-membered ring or hexa-atomic ring substituents being all made of carbon atom, Huo Zheyou The five-membered ring or hexa-atomic ring substituents that any one and carbon atom in oxygen, nitrogen and silicon atom form together；The substituted ring When substituent group on shape substituent group is preferably the ester group of 1-20 carbon atom, Formula II compound represented is particularly suitable for solar energy Field of batteries or lithium-air battery field further can be used as the photosensitizer of solar battery or answer as lithium storage materials For in lithium-air battery.

In formula IV compound represented, R₂To indicate number 1,2,3,7 or 8, the substituent group in number 8, R are preferably indicated₂It is excellent It is selected as the alkoxy of 1-20 carbon atom；It indicates in the position 2,3-, the position 3,4-, the position 4,5- and the position 5,6- of digital 1-6 Any one, substituted or unsubstituted cyclic substituents at the position preferably 4,5-；The cyclic substituents are preferably all Four-membered ring, five-membered ring or the hexa-atomic ring substituents being made of carbon atom, or by any one and the carbon in oxygen, nitrogen and silicon atom When four-membered ring, five-membered ring or hexa-atomic ring substituents that atom forms together；Formula IV compound represented is particularly suitable for light power Learn treatment.

In Formula V compound represented, R₂To indicate at least one of number 1,2,3,7,8 and 9, number is preferably indicated Substituent group on 8 and 9, R₂The alkoxy of preferably 1-20 carbon atom or the ester group of 1-20 carbon atom；Indicate digital 1-6's 2,3- positions, the position 3,4-, the position 4,5- and 5, any one in the position 6- are substituted or unsubstituted at the position preferably 4,5- Cyclic substituents；The cyclic substituents are preferably the five-membered ring or hexa-atomic ring substituents being all made of carbon atom, or The five-membered ring or hexa-atomic ring substituents being made of together any one and the carbon atom in oxygen, nitrogen and silicon atom；It is described substituted Substituent group on cyclic substituents is preferably the ester group of 1-20 carbon atom；When Y is-O- or-S-；Formula V compound represented is outstanding It is suitable for photodynamic therapy for cancer.

In Formula IV compound represented, R₂For indicate number 1,2,3,7 or 8 on, preferably indicate number 8 on substituent group, And R₂For aryl, preferably phenyl；Indicate appointing in the position 2,3-, the position 3,4-, the position 4,5- and the position 5,6- of digital 1-6 It anticipates one, substituted or unsubstituted cyclic substituents at the position preferably 4,5-；The cyclic substituents are preferably all by carbon Former molecular five-membered ring or hexa-atomic ring substituents, or by any one and the carbon atom in oxygen, nitrogen and silicon atom together group At five-membered ring or hexa-atomic ring substituents；Substituent group on the substituted cyclic substituents is preferably the ester of 1-20 carbon atom When base；Formula IV compound represented is particularly suitable for area of solar cell, further, can be used as the photosensitive of solar battery Agent.

In formula III compound represented, R₂To indicate the substituent group on digital 1-6, R₂Preferably H；Indicate digital 1-6's 2,3- positions, the position 3,4-, the position 4,5- and 5, any one in the position 6- are substituted or unsubstituted at the position preferably 4,5- Cyclic substituents；The cyclic substituents are preferably the five-membered ring or hexa-atomic ring substituents being all made of carbon atom, or The five-membered ring or hexa-atomic ring substituents being made of together any one and the carbon atom in oxygen, nitrogen and silicon atom；It is described substituted Substituent group on cyclic substituents is preferably the ester group of 1-20 carbon atom；When X is-O- or-S-；Formula III compound represented It is particularly suitable for photodynamic therapy for cancer.

In Formulas I ' compound represented, R₃To indicate the substituent group on digital 1-6, R₃Preferably H；The 2 of digital 1-6 are indicated, The position 3-, the position 3,4-, the position 4,5- and 5, any one in the position 6- are substituted or unsubstituted at the position preferably 4,5- Cyclic substituents；The cyclic substituents are preferably the five-membered ring or hexa-atomic ring substituents being all made of carbon atom, Huo Zheyou When five-membered ring or hexa-atomic ring substituents that any one and carbon atom in oxygen, nitrogen and silicon atom form together, Formulas I ' shown in Compound is particularly suitable for area of solar cell, further, can be used as the photosensitizer of solar battery.

In Formula II ' compound represented, R₃To indicate the substituent group on digital 1-6, R₃Preferably H；Indicate digital 1-6's 2,3- positions, the position 3,4-, the position 4,5- and 5, any one in the position 6- are substituted or unsubstituted at the position preferably 4,5- Cyclic substituents；The cyclic substituents are preferably the five-membered ring or hexa-atomic ring substituents being all made of carbon atom, or When the five-membered ring or hexa-atomic ring substituents that are made of together any one and the carbon atom in oxygen, nitrogen and silicon atom, Formula II ' shown in Compound be particularly suitable for area of solar cell, further, can be used as the photosensitizer of solar battery.

In formula III ' compound represented, R₃To indicate the substituent group on digital 1-6, R₃For aryl, preferably phenyl；Mark There are the position 2,3-, the position 3,4-, the position 4,5- and 5 of digital 1-6, any one in the position 6-, preferably 4,5- has at position Substituted or unsubstituted cyclic substituents；The cyclic substituents are preferably the five-membered ring or hexatomic ring being all made of carbon atom Substituent group, or the five-membered ring or hexa-atomic ring substituents that are made of together any one and the carbon atom in oxygen, nitrogen and silicon atom； X isWhen, formula III ' compound represented is particularly suitable for photodynamic therapy for cancer.

In formula IV ' compound represented, R₃To indicate the substituent group on digital 1-8, R₃For aryl, preferably phenyl；It indicates The position 2,3-, the position 3,4-, the position 4,5- and 5 of digital 1-6, any one in the position 6-, preferably 4,5- takes at position Generation or unsubstituted cyclic substituents；The cyclic substituents are preferably that the five-membered ring or hexatomic ring being all made of carbon atom take Dai Ji, or the five-membered ring or hexa-atomic ring substituents that are made of together any one and the carbon atom in oxygen, nitrogen and silicon atom；Institute State the ester group that the substituent group on substituted cyclic substituents is preferably 1-20 carbon atom；X isWhen, formula IV ' shown in Compound be particularly suitable for photodynamic therapy for cancer.

In Formula V ' compound represented, R₃To indicate the substituent group on digital 1-9, R₃For the alkyl of 1-20 carbon atom；Mark There are the position 2,3-, the position 3,4-, the position 4,5- and 5 of digital 1-6, any one in the position 6-, preferably 4,5- has at position Substituted or unsubstituted cyclic substituents；The cyclic substituents are preferably the five-membered ring or hexatomic ring being all made of carbon atom Substituent group, or the five-membered ring or hexa-atomic ring substituents that are made of together any one and the carbon atom in oxygen, nitrogen and silicon atom； Substituent group on the substituted cyclic substituents is preferably the ester group of 1-20 carbon atom；When Y is-O- or-S-, Formula V ' shown in Compound be particularly suitable for photodynamic therapy for cancer.

In Formula IV ' compound represented, R₃To indicate the substituent group on digital 1-8, R₃For the alcoxyl of 1-20 carbon atom Base；The position 2,3-, the position 3,4-, the position 4,5- and 5 of digital 1-6 are indicated, any one in the position 6-, the position preferably 4,5- Locate substituted or unsubstituted cyclic substituents；The cyclic substituents are preferably the five-membered ring or six being all made of carbon atom First ring substituents, or the five-membered ring or hexatomic ring that are made of together any one and the carbon atom in oxygen, nitrogen and silicon atom take Dai Ji；When substituent group on the substituted cyclic substituents is preferably the ester group of 1-20 carbon atom, Formula IV ' shown in chemical combination Object is particularly suitable for photodynamic therapy for cancer.

It below will the present invention will be described in detail by specific embodiment.

In following embodiment, used specific Formula VII, Formula VIII and Formula IX compound represented are respectively according to as follows Method preparation in preparation example.

Preparation example 1

Wherein, TMS represents trimethyl silicon substrate.EtMgBr is that ethylmagnesium bromide (is purchased from lark prestige Science and Technology Ltd., commodity The trade mark be 248474),(trimethyl silicane acraldehyde, is purchased from lark prestige Science and Technology Ltd., and trade names are 2975-46-4), (n-Bu)₄NF (tetra-n-butyl ammonium fluoride is purchased from lark prestige Science and Technology Ltd., trade names A10588).

(1) preparation of compound 1

Under nitrogen atmosphere, under magnetic stirring, 1,6- heptadiyne, (5.0mL, 4.02g, 43.63mmol are purchased from me Fourth reagent (Shanghai) Co., Ltd., trade names H102744-25mL) it is dissolved in 100mL tetrahydrofuran, it is cooled to 0 DEG C, by It is added dropwise to ethyl phosphonium bromide magnesium solution (tetrahydrofuran solution of 1.0M, 43.6mL contain ethylmagnesium bromide 43.60mmol), adds in 1h It is complete, it is cooled to 0 DEG C after reacting 1h at room temperature, is rapidly joined trimethyl silicane acraldehyde (7.30mL, 43.60mmol), is continued anti- Answer 1h, after reaction, be quenched with saturated ammonium chloride solution, ether extraction merges organic phase, and anhydrous magnesium sulfate dries, filters, Concentration, silica gel column chromatography (eluant, eluent: n-hexane/ethyl acetate=6/1 volume ratio) obtain 5.71g colourless oil liquid compound 1, yield: 60%.(mole/1,6- heptadiyne mole × 100% that the yield of compound 1 is compound 1).

The nuclear-magnetism and high resolution mass spectrum data of compound 1 are as follows:

¹δ=5.04 H NMR (t, J=1.80Hz, 1H), 2.69 (br, 1H), 2.31 (td, J=6.99Hz, J= 1.80Hz, 2H), 2.25 (td, J=6.99Hz, J=2.60Hz, 2H), 1.93 (t, J=2.60Hz, 1H), 1.69 (m, 2H), 0.14(s,9H)；¹³C NMR δ=102.71,88.81,84.24,83.45,78.31,69.12,52.59,27.25,17.82, 17.56, -0.26.HRMS-ESI (m/z) calculated value C₁₃H₁₈OSiNa[M+Na]⁺241.1019 actual value 241.1025.

(2) preparation of compound 2

Compound 1 (5.00g, 22.90mmol) is dissolved in 120mL tetrahydrofuran, is cooled to 0 DEG C, is slowly added into four positive fourths Base ammonium fluoride solution (tetrahydrofuran solution of 1.0M, 27.48mL, the ammonium fluoride 27.48mmol containing tetra-n-butyl), reaction to raw material It disappears (30min), reaction solution is quenched with saturated ammonium chloride solution, and ether extraction, organic phase is dry with anhydrous magnesium sulfate, then passes through Column chromatography separates (eluant, eluent: n-hexane/ethyl acetate=4/1 volume ratio) and obtains 2.85g colourless oil liquid compound 2, produces Rate: 85%.(mole × 100% that the yield of compound 2 is mole/compound 1 of compound 2).

The nuclear-magnetism and high resolution mass spectrum data of compound 2 are as follows:

¹δ=5.08 H NMR (m, 1H), 2.69 (br, 1H), 2.53 (t, J=2.20Hz, 1H), 2.34 (td, J= 7.00Hz, J=1.85Hz, 2H), 2.25 (td, J=7.00Hz, J=2.57Hz, 2H), 1.95 (t, J=2.57Hz, 1H), 1.71(m,2H)；¹³C NMR δ=84.65,83.49,81.52,77.91,72.39,69.22,52.06,27.18,17.77, 17.62.HRMS-ESI (m/z) calculated value C₁₀H₁₀OSiNa[M+Na]⁺169.0624 actual value 169.0651.

Preparation example 2

Wherein, n-BuLi is n-BuLi (being purchased from lark prestige Science and Technology Ltd., trade names 913796).

(1) preparation of compound 3

Under nitrogen atmosphere, under magnetic stirring, 2,2- dipropargyl dimethyl malenate (5.00g, 24.0mmol, According to document J.Am.Chem.Soc.2013,135,8133. synthesis) it is dissolved in 200mL tetrahydrofuran, -78 DEG C are cooled to, dropwise It is added n-BuLi (tetrahydrofuran solution of 2.2M, 10.90mL contain n-BuLi 24.0mmol), is added in 1h, at -78 DEG C After reacting 15min, trimethyl silicane acraldehyde (3.52mL, 24.0mmol) is added dropwise, the reaction was continued, and 2h is used after reaction Saturated ammonium chloride solution is quenched, and ether extraction merges organic phase, and anhydrous magnesium sulfate dries, filters, and is concentrated, and silica gel column chromatography (is washed De- agent: n-hexane/ethyl acetate=5/1 volume ratio), obtain 4.82g pale yellow oily liquid compound 3, yield: 60%.(chemical combination The yield of object 3 is mole/2,2- dipropargyl dimethyl malenate mole × 100% of compound 3).

The nuclear-magnetism and high resolution mass spectrum data of compound 3 are as follows:

¹δ=5.03 H NMR (s, 1H), 3.76 (s, 6H), 3.03 (d, J=2.00Hz, 2H), 2.97 (d, J=2.64Hz, 2H), 2.37 (br, 1H), 2.03 (t, J=2.60Hz, 1H), 0.19 (s, 9H)；¹³C NMR δ=169.05,102.11,88.97, 81.08,79.06,78.28,71.88,56.59,53.14,52.30,22.93,22.77,-0.41；HRMS-ESI (m/z) is calculated Value C₁₇H₂₂O₅SiNa[M+Na]⁺357.1129 actual value 357.1130.

(2) preparation of compound 4

Compound 3 (4.82g, 14.4mmol) is dissolved in 150mL tetrahydrofuran, is cooled to -30 DEG C, is being slowly added into four just Butyl ammonium fluoride solution (tetrahydrofuran solution of 1.0M, 21.6mL, the ammonium fluoride 21.6mmol containing tetra-n-butyl), reaction to raw material It disappears (20min), reaction solution is quenched with saturated ammonium chloride solution, and ether extraction, organic phase is dry with anhydrous magnesium sulfate, then passes through Column chromatography separates (eluant, eluent: n-hexane/ethyl acetate=3/1 volume ratio) and obtains 3.21g pale yellow oily liquid compound 4, Yield: 85%.(mole × 100% that the yield of compound 4 is mole/compound 3 of compound 4).

The nuclear-magnetism and high resolution mass spectrum data of compound 4 are as follows:

¹δ=5.05 H NMR (ddt, J=7.51Hz, J=2.25Hz, J=2.11Hz, 1H), 3.76 (s, 1H), 3.02 (d, J=2.11Hz, 2H), 2.95 (d, J=2.72Hz, 2H), 2.81 (d, J=7.51Hz, 1H), 2.53 (d, J=2.25Hz, 1H), 2.03 (t, J=2.68Hz, 1H)；¹³C NMR δ=169.11,80.99,80.78,79.03,78.19,72.44,72.10, 56.48,53.25,51.54,22.84,22.75；HRMS-ESI (m/z) calculated value C₁₄H₁₄O₅Na[M+Na]⁺285.0733, it is practical Value 285.0734.

Preparation example 3

(1) in addition to following characteristics, the preparation method of compound 5 is identical as the preparation method of compound 1.

The propine ether that 1,6- heptadiyne used in preparation example 1 changes equimolar number into (is changed purchased from AlfaAesar (China) Learn Co., Ltd, trade names MFCD00048108).

The yield of compound 5: 75%.(yield of compound 5 be compound 5 mole/alkynes propyl ether mole × 100%).

The nuclear-magnetism and high resolution mass spectrum data of compound 5 are as follows:

¹δ=5.14 H NMR (t, J=1.67Hz, 1H), 4.31 (d, J=1.67Hz, 1H), 4.24 (b, J=2.37Hz, 2H), 2.47 (br, 1H), 2.46 (t, J=2.37Hz, 1H), 0.17 (s, 9H)；¹³C NMR δ=101.60,89.95,84.19, 79.74,78.85,75.40,56.81,56.75,52.59,-0.22；HRMS-ESI (m/z) calculated value C₁₂H₁₆O₂SiNa[M+Na ]⁺243.0812 actual value 248.0805.

(2) in addition to following characteristics, the preparation method of compound 6 is identical as the preparation method of compound 2.

Compound 1 used in 1 step of preparation example (2) is changed into the compound 5 obtained in this preparation example step (1).

The yield of compound 6: 87%.(yield of compound 6 be compound 6 mole/compound 5 mole × 100%).

The nuclear-magnetism and high resolution mass spectrum data of compound 6 are as follows:

¹δ=5.16 H NMR (s, 1H), 2.69 (br, 1H), 4.31 (d, J=1.52Hz, 1H), 4.25 (d, J= 2.25Hz, 2H), 2.80 (br, 2H), 2.57 (d, J=2.25Hz, 1H), 2.47 (t, J=2.25Hz, 1H)；¹³C NMR δ= 83.81,80.69,80.09,78.82,75.47,73.13,56.87,56.76,52.05；HRMS-ESI (m/z) calculated value C₉H₈O₂Na[M+Na]⁺171.0417 actual value 171.0411.

Preparation example 4

(1) in addition to following characteristics, the preparation method of compound 7 is identical as the preparation method of compound 3.

By trimethyl silicane propargyl aldehyde used in preparation example 2 change into equimolar number 1- phenyl -2- propine -1- ketone (according to Document Guang-Cun Ge, Dong-Liang Mo, Chang-Hua Ding, Li-Xin Dai, Xue-Long Hou, Palladacycle-Catalyzed Reaction of Bicyclic Alkenes with Terminal Ynones: Regiospecific Synthesis of Polysubstituted Furans, Org.Lett.2012,14,5756 synthesis).

The yield of compound 7: 75%.(yield of compound 7 is mole/2,2- dipropargyl malonic acid of compound 7 Mole × 100% of dimethyl ester).

The nuclear magnetic data of compound 7 is as follows:

¹H NMR δ=7.29-7.47 (m, 5H), 3.75 (s, 6H), 3.02 (s, 2H), 2.96 (d, J=2.63Hz, 2H), 2.50 (br, 1H), 2.11 (s, 1H), 2.02 (t, J=2.63Hz, 1H)；¹³C NMR δ=169.14,132.54,129.15, 128.34,121.41,89.07,81.18,79.07,78.29,75.23,71.89,56.60,53.15,52.31,22.94, 22.78；

Preparation example 5

(1) in addition to following characteristics, the preparation method of compound 8 is identical as the preparation method of compound 1.

1,6- heptadiyne used in preparation example 1 is changed the 1- propynyloxy base -2- butine of equimolar number into (according to document Hong-Tai Chang,Masilamani Jeganmohan,Chien-Hong Cheng,Cobalt-Catalyzed Intramolecular[2+2+2]Cocyclotrimerization of Nitrilediynes:An Efficient Route To Tetra-and Pentacyclic Pyridine Derivatives, Org.Lett.2007,9,505 synthesis).

The yield of compound 8: 82%.(yield of compound 8 is mole/1- propynyloxy base -2- butine of compound 8 Mole × 100%).

The nuclear magnetic data of compound 8 is as follows:

¹δ=5.13 H NMR (t, J=1.68Hz, 1H), 4.32 (d, J=1.68Hz, 1H), 4.25 (q, J=1.65Hz, 2H), 2.48 (br, 1H), 1.80 (t, J=1.65Hz, 3H), 0.16 (s, 9H)；¹³C NMR δ=101.49,89.94,84.18, 79.73,78.84,75.39,56.80,56.14,52.48,3.80,-0.21.

(2) in addition to following characteristics, the preparation method of compound 9 is identical as the preparation method of compound 2.

Compound 1 used in 1 step of preparation example (2) is changed into the compound 8 obtained in this preparation example step (1).

The yield of compound 9: 86%.(yield of compound 9 be compound 9 mole/compound 8 mole × 100%).

The nuclear magnetic data of compound 9 is as follows:

¹δ=5.12 H NMR (s, 1H), 4.30 (d, J=1.51Hz, 1H), 4.24 (q, J=1.54Hz, 2H), 2.85 (br, 1H), 2.56 (d, J=2.24Hz, 1H), 1.75 (t, J=1.54Hz, 1H)；¹³C NMR δ=83.80,80.68,80.08, 78.71,75.36,73.02,56.76,56.65,52.17,3.85.

Preparation example 6

(1) in addition to following characteristics, the preparation method of compound 13 is identical as the preparation method of compound 3.

2,2- dipropargyl dimethyl malenate used in preparation example 2 is changed into 4- propynyloxy base -1 of equimolar number, 2- butadiene is (according to document Hongwen Luo, Shengming Ma, CuI-Catalyzed Synthesis of Functionalized Terminal Allenes from 1-Alkynes, Eur.J.Org.Chem.2013,15,3041. and PCT Int.Appl., 2011050016 synthesis).

Compound 13 is pale yellow oily liquid, yield: 55%.(yield of compound 13 be compound 13 mole/ Mole × 100% of 4- propynyloxy base -1,2- butadiene).

The nuclear-magnetism and high resolution mass spectrum data of compound 13 are as follows:

¹δ=5.20 H NMR (tt, J=6.69Hz, J=6.69Hz, 1H), 5.15 (t, J=1.84,1H), 4.78 (dt, J =6.69Hz, J=2.34Hz, 2H), 4.23 (d, J=1.84Hz, 2H), 4.12 (dt, J=6.69Hz, J=2.34Hz, 2H), 2.68(br,1H),0.11(s,9H)；¹³C NMR δ=209.36,101.23,86.51,83.24,80.67,80.12,75.67, 72.53,67.32,56.91,52.35；HRMS-ESI (m/z) calculated value C₁₃H₁₈O₂SiNa[M+Na]⁺257.0968, actual value 257.0986.

(2) in addition to following characteristics, the preparation method of compound 14 is identical as the preparation method of compound 4.

Compound 3 used in 2 step of preparation example (2) is changed into the compound 13 obtained in this preparation example step (1).

Compound 14 is pale yellow oily liquid, yield: 92%.(yield of compound 14 be compound 14 mole/ Mole × 100% of compound 13).

The nuclear-magnetism and high resolution mass spectrum data of compound 14 are as follows:

¹δ=5.22 H NMR (tt, J=6.71Hz, J=6.71Hz, 1H), 5.16 (dt, J=1.84Hz, J=1.84, 1H), 4.81 (dt, J=6.71Hz, J=2.35Hz, 2H), 4.23 (d, J=1.84Hz, 2H), 4.09 (dt, J=6.71Hz, J =2.35Hz, 2H), 2.71 (br, 1H), 2.57 (d, J=1.84Hz, 1H)；¹³C NMR δ=209.57,86.81,83.45, 80.77,80.13,76.01,72.81,67.46,56.81,51.50；HRMS-ESI (m/z) calculated value C₁₀H₁₀O₂Na[M+Na]⁺ 185.0573 actual value 185.0574.

Preparation example 7

(1) in addition to following characteristics, the preparation method of compound 15 is identical as the preparation method of compound 3.

2,2- dipropargyl dimethyl malenate used in preparation example 2 is changed into the 2- propargyl -2- (5- of equimolar number Phenyl -2,4- pentadiine base) dimethyl malenate is (according to document Wei Shi, Yingdong Luo, Xiancai Luo, Lei Chao,Heng Zhang,Jian Wang,Aiwen Lei,Investigation of an Efficient Palladium- Catalyzed C(sp)-C(sp)Cross-Coupling Reaction Using Phosphine-Olefin Ligand: Application and Mechanistic Aspects, J.Am.Chem.Soc.2008,130,14713. synthesis).

Compound 15 is faint yellow solid, yield: 45%.(yield of compound 15 is mole/2- alkynes of compound 15 Mole × 100% of propyl -2- (5- phenyl -2,4- pentadiine base) dimethyl malenate).

The nuclear-magnetism and high resolution mass spectrum data of compound 15 are as follows:

¹H NMR δ=7.30-7.48 (m, 5H), 5.04 (dt, J=7.61Hz, J=2.02Hz, 1H), 3.79 (s, 6H), 3.16 (s, 2H), 3.07 (d, J=2.02Hz, 2H), 2.35 (d, J=7.61Hz, 1H), 0.19 (s, 9H)；¹³C NMR δ= 168.86,132.57,129.16,128.56,101.99,89.28,81.30,79.12,77.82,75.92,68.30,56.73, 53.29,52.45,24.06,23.29,-0.36；HRMS-ESI (m/z) calculated value C₂₅H₂₆O₅SiNa[M+Na]⁺457.1442, it is real Actual value 457.1450.

(2) in addition to following characteristics, the preparation method of compound 16 is identical as the preparation method of compound 4.

Compound 3 used in 2 step of preparation example (2) is changed into the compound 15 obtained in this preparation example step (1).

Compound 16 is faint yellow solid, yield: 89%.(yield of compound 16 is mole/chemical combination of compound 16 Mole × 100% of object 15).

The nuclear-magnetism and high resolution mass spectrum data of compound 16 are as follows:

¹H NMR δ=7.29-7.48 (m, 5H), 5.07 (dt, J=2.25, J=2.29,1H), 3.80 (s, 6H), 3.16 (s, 2H), 3.07 (d, J=2.29Hz, 2H), 2.55 (d, J=2.25Hz, 1H), 2.19 (br, 1H)；¹³δ=168.89 C NMR, 132.59,129.20,128.40,121.52,80.93,79.33,77.74,75.99,73.78,72.56,68.37,56.67, 53.39,51.86,24.10,23.25；HRMS-ESI (m/z) calculated value C₂₂H₁₈O₅Na[M+Na]⁺385.1046, actual value 385.1049.

Preparation example 8

In addition to following characteristics, the preparation method of compound 17 is identical as the preparation method of compound 1.

By trimethyl silicane propargyl aldehyde used in preparation example 1 change into equimolar number 1- phenyl -2- propine -1- ketone (according to Document Guang-Cun Ge, Dong-Liang Mo, Chang-Hua Ding, Li-Xin Dai, Xue-Long Hou, Palladacycle-Catalyzed Reaction of Bicyclic Alkenes with Terminal Ynones: Regiospecific Synthesis of Polysubstituted Furans, Org.Lett.2012,14,5756 synthesis).

The yield of compound 17: 61%.(yield of compound 17 be 17 moles/1,6- heptadiyne mole × 100%).

The nuclear magnetic data of compound 17 is as follows:

¹H NMR δ=7.31-7.49 (m, 5H), 2.65 (br, 1H), 2.41 (s, 1H), 2.32 (t, J=6.98Hz, 2H), 2.23 (td, J=6.98Hz, J=2.55Hz, 2H), 1.97 (t, J=2.55Hz, 1H), 1.69 (m, 2H)；¹³C NMR δ= 132.53,129.14,128.34,121.48,84.61,83.45,81.48,77.87,72.35,69.47,52.12,27.14, 17.72,17.58.

Preparation example 9

(1) in addition to following characteristics, the preparation method of compound 18 is identical as the preparation method of compound 1.

By 1,6- heptadiyne used in embodiment 1 change into equimolar number 1,8- nonyl diine (purchased from AlfaAesar (in State) Chemical Co., Ltd., trade names MFCD00008581).

The yield of compound 18: 47%.(yield of compound 18 is that mole/1,8- nonyl diine of compound 18 rubs You measure × 100%).

The nuclear magnetic data of compound 18 is as follows:

¹δ=5.04 H NMR (t, J=1.85Hz, 1H), 2.58 (br, 1H), 2.22 (td, J=6.99Hz, J= 1.85Hz, 2H), 2.17 (td, J=6.99Hz, J=2.83Hz, 2H), 1.92 (t, J=2.83Hz, 1H), 1.60 (m, 6H), 0.14(s,9H)；¹³C NMR δ=102.59,88.72,84.88,84.02,77.58,68.64,52.51,27.36,27.10, 18.15,17.04,16.98,-0.25.

(2) in addition to following characteristics, the preparation method of compound 19 is identical as the preparation method of compound 2.

Compound 1 used in 1 step of embodiment (2) is changed into the compound 18 obtained in the present embodiment step (1).

The yield of compound 19: 80%.(yield of compound 19 is mole of mole/compound 18 of compound 19 Amount × 100%).

The nuclear magnetic data of compound 19 is as follows:

¹δ=5.05 H NMR (d, J=2.22Hz, 1H), 2.87 (br, 1H), 2.51 (d, J=2.22Hz, 1H), 2.20 (td, J=6.78Hz, J=1.94Hz, 2H), 2.16 (td, J=6.75Hz, J=2.56Hz, 2H, 2H), 1.97 (d, J= 2.56Hz,1H),1.62(m,6H)；¹³C NMR δ=85.18,84.11,76.74,72.38,68.87,51.82,27.35, 27.07,18.11,17.85,17.52.

Preparation example 10

(1) in addition to following characteristics, the preparation method of compound 20 is identical as the preparation method of compound 3.

2,2- dipropargyl dimethyl malenate used in preparation example 2 is changed into the HC ≡ CCH of equimolar number₂C (COOMe)₂CH₂CH=C=CH₂(according to documentRamaiah Kumareswaran,Seunghoon Shin,Isabelle Gallou,and T.V.RajanBabu,Silylstannylation of Allenes and Silylstannylation- Cyclization of Allenynes.Synthesis of Highly Functionalized Allylstannanes And Carbocyclic and Heterocyclic Compounds, J.Org.Chem.2004,69,7157 synthesis).

Compound 20 is pale yellow oily liquid, yield: 60%.(yield of compound 20 be compound 20 mole/ HC≡CCH₂C(COOMe)₂CH₂CH=C=CH₂Mole × 100%).

The nuclear magnetic data of compound 20 is as follows:

¹δ=5.05 H-NMR (t, J=1.85Hz, 1H), 4.95 (tt, J=8.00Hz, J=6.64Hz, 1H), 4.71 (dt, J=6.64Hz, J=2.41Hz, 2H), 3.74 (s, 6H), 2.90 (dt, J=8.00Hz, J=2.41Hz, 1H), 2.70 (dt, J=7.95Hz, J=2.41Hz, 1H), 2.30 (br, 1H)；¹³C NMR δ=210.12,170.07,102.18,88.79, 83.65,80.85,79.42,74.82,57.23,52.82,52.30,31.80,22.97,-0.39.

(2) in addition to following characteristics, the preparation method of compound 21 is identical as the preparation method of compound 4.

Compound 3 used in 2 step of preparation example (2) is changed into the compound 20 obtained in this preparation example step (1).

Compound 21 is pale yellow oily liquid, yield: 93%.(yield of compound 21 be compound 21 mole/ Mole × 100% of compound 20).

The nuclear magnetic data of compound 21 is as follows:¹δ=5.07 H-NMR (br, 1H), 4.97 (m, 1H), 4.71 (dt, J= 6.66Hz, J=2.44Hz, 2H), 3.77 (s, 6H), 2.92 (d, J=2.00Hz, 1H), 2.77 (dt, J=8.01Hz, J= 2.44Hz, 1H), 2.55 (d, J=2.40Hz, 1H), 2.54 (br, 1H)；¹³C NMR δ=210.07,170.10,83.60, 81.11,80.57,79.49,74.84,73.28,57.10,52.86,51.61,31.80,22.91.

Preparation example 11

(1) in addition to following characteristics, the preparation method of compound 22 is identical as the preparation method of compound 3.

2,2- dipropargyl dimethyl malenate used in preparation example 2 is changed into the HC ≡ CCH of equimolar number₂C (COOMe)₂CH₂CH=C=CHPh is (according to document Ramaiah Kumareswaran, Seunghoon Shin, Isabelle Gallou,and T.V.RajanBabu,Silylstannylation of Allenes and Silylstannylation- Cyclization of Allenynes.Synthesis of Highly Functionalized Allylstannanes And Carbocyclic and Heterocyclic Compounds, J.Org.Chem.2004,69,7157 synthesis).

Compound 22 is pale yellow oily liquid, yield: 62%.(yield of compound 22 be compound 22 mole/ HC≡CCH₂C(COOMe)₂CH₂Mole × 100% of CH=C=CHPh).

The nuclear magnetic data of compound 22 is as follows:

¹H-NMR δ=7.30-7.49 (m, 5H), 5.02 (t, J=1.84Hz, 1H), 4.93 (td, J=7.95Hz, J= 6.61Hz, 1H), 4.71 (dt, J=6.61Hz, J=2.28Hz, 2H), 3.72 (s, 6H), 2.88 (d, J=1.84Hz, 1H), 2.68 (dt, J=7.95Hz, J=2.38Hz, 1H), 2.28 (br, 1H), 0.19 (s, 1H)；¹³δ=210.09 C NMR, 170.05,132.54,129.15,128.35,121.47,102.13,88.74,83.61,80.81,79.37,74.77, 57.12,52.85,52.32,31.65,22.95,-0.25.

(2) in addition to following characteristics, the preparation method of compound 23 is identical as the preparation method of compound 4.

Compound 3 used in 2 step of preparation example (2) is changed into the compound 22 obtained in this preparation example step (1).

Compound 23 is pale yellow oily liquid, yield: 93%.(yield of compound 23 be compound 23 mole/ Mole × 100% of compound 22).

The nuclear magnetic data of compound 23 is as follows:

¹H-NMR δ=7.35-7.54 (m, 5H), 5.12 (br, 1H), 4.92 (tt, J=8.01Hz, J=6.63Hz, 1H), 4.76 (dt, J=6.63Hz, J=2.43Hz, 2H), 3.75 (s, 6H), 2.97 (d, J=2.01Hz, 1H), 2.72 (dt, J= 8.01Hz, J=2.43Hz, 1H), 2.45 (d, J=2.39Hz, 1H), 2.40 (br, 1H)；¹³C NMR δ=210.17,170.17, 132.64,129.35,128.45,121.58,83.62,81.41,80.64,79.63,74.92,73.34,57.25,52.74, 51.53,31.94,22.73.

Preparation example 12

(1) in addition to following characteristics, the preparation method of compound 24 is identical as the preparation method of compound 3.

2,2- dipropargyl dimethyl malenate used in preparation example 2 is changed into the 2- propargyl -2- (5- of equimolar number (2- thienyl) -2,4- pentadiine base) dimethyl malenate is (according to document Wei Shi, Yingdong Luo, Xiancai Luo,Lei Chao,Heng Zhang,Jian Wang,Aiwen Lei,Investigation of an Efficient Palladium-Catalyzed C(sp)-C(sp)Cross-Coupling Reaction Using Phosphine-Olefin Ligand:Application and Mechanistic Aspects, J.Am.Chem.Soc.2008,130,14713. conjunction At).

Compound 24 is faint yellow solid, yield: 47%.(yield of compound 24 is mole/2- alkynes of compound 24 Mole × 100% of propyl -2- (5- (2- thienyl) -2,4- pentadiine base) dimethyl malenate).

The nuclear magnetic data of compound 24 is as follows:

¹H NMR δ=7.16-7.48 (m, 3H), 5.03 (dt, J=7.60Hz, J=2.03Hz, 1H), 3.77 (s, 6H), 3.14 (s, 2H), 3.08 (d, J=2.03Hz, 2H), 2.34 (d, J=7.60Hz, 1H), 0.18 (s, 9H)；¹³C NMR δ= 170.21,132.57,128.16,127.56,122.31,101.91,89.07,81.32,79.04,77.75,75.85, 68.24,56.65,53.47,52.53,24.14,23.31,-0.31.

(2) in addition to following characteristics, the preparation method of compound 25 is identical as the preparation method of compound 4.

Compound 3 used in 2 step of preparation example (2) is changed into the compound 24 obtained in this preparation example step (1).

Compound 25 is faint yellow solid, yield: 83%.(yield of compound 25 is mole/chemical combination of compound 25 Mole × 100% of object 24).

The nuclear magnetic data of compound 25 is as follows:

¹H NMR δ=7.18-7.46 (m, 3H), 5.08 (dt, J=2.25, J=2.29,1H), 3.81 (s, 6H), 3.12 (s, 2H), 3.01 (d, J=2.29Hz, 2H), 2.54 (d, J=2.25Hz, 1H), 2.13 (br, 1H)；¹³δ=169.99 C NMR, 132.42,129.11,128.42,121.25,80.37,79.76,77.56,75.47,73.85,72.86,68.14,56.16, 53.35,51.45,24.28,23.46.

Embodiment 1

Preparation method of the present embodiment to metal bridge location fused ring compound shown in formula I.

In above formula, [Ru]¹For RuCl (PPh₃)₂, PPh₃For triphenylphosphine, DCM is methylene chloride, and Me is methyl.

Under nitrogen atmosphere, under magnetic stirring, toward RuCl₂(PPh₃)₃(1.40g, 1.46mmol) and PPh₃(1.91g, HC ≡ CCH made from preparation example 2 is added dropwise in methylene chloride (dosage of methylene chloride is 20mL) solution 7.3mmol) (OH)C≡CCH₂C(COOMe)₂CH₂The methylene chloride (dosage of methylene chloride is 2mL) of C ≡ CH (0.57g, 2.19mmol) is molten Liquid, reacts 1h at room temperature, and solution colour is red.Reaction solution is concentrated into 5mL with vacuum pump, then washs (washing with n-hexane Three times, each 50mL) 1.23g red solid compound I-1, yield: 70% (yield of compound I-1 be compound I-1 Mole/RuCl₂(PPh₃)₃Mole × 100%).

The spectral data of metal bridge location fused ring compound obtained is as follows:

¹H NMR(300.1MHz,CD₂Cl₂): δ=13.06 (s, 1H, C⁷H),7.33(1H,C³H),6.99-7.81(46H, Phenyl and C³H),3.64(s,6H,COOCH₃), 2.96 (t, J (H, H)=3.63, C¹⁰H),2.76(s,C⁸H)；³¹P{¹H}NMR (121.5MHz,CD₂Cl₂): δ=29.59 (d, J (P, P)=5.89Hz, RuPPh₃), 6.38 (t, J (P, P)=5.89Hz, CPPh₃)；¹³C{¹H}NMR(75.5MHz,CD₂Cl₂): δ=356.95 (br, C¹), 251.89 (t, J (P, C)=11.96, C⁷), 190.23 (dt, J (P, C)=25.65Hz, J (P, C)=4.90Hz, C⁴), 180.98 (d, J (P, C)=1.97Hz, C⁵), 171.77(s,COOCH₃), 164.57 (t, J (P, C)=4.24Hz, C⁶), 154.99 (dt, J (P, C)=14.44Hz, J (P, C) =3.07Hz, C³), 128.18-135.76 (other aromatic carbons), 122.86 (dt, J (P, C)=92.99Hz, J (P, C)= 4.02Hz,C²), 119.57 (aromatic carbons), 64.14 (s, C⁹),53.63(s,COOCH₃),39.06(s,C⁸),37.35(s,C¹⁰)； HRMS (ESI): m/z theoretical value [C₆₈H₅₇ClO₄P₃Ru]⁺,1167.2212；Measured value 1167.2215.

Embodiment 2

In above formula, [Ru]¹For RuCl (PPh₃)₂。

In addition to following characteristics, the preparation method of compound I-3 is identical as the preparation method of compound I-1 in embodiment 1:

By HC ≡ CCH (OH) C ≡ CCH used in embodiment 1₂C(COOMe)₂CH₂C ≡ CH changes the preparation of equimolar number into HC ≡ CCH (OH) C ≡ CCH made from example 3₂OCH₂C≡CH。

Red solid compound I-3 is obtained, yield: 68% (mole that the yield of compound I-3 is compound I-3/ RuCl₂(PPh₃)₃Mole × 100%).

¹H NMR(300.1MHz,CD₂Cl₂): δ=13.17 (s, 1H, C⁷H),7.35(s,1H,C³H),7.01-7.81 (46H, phenyl and C³H),4.36(s,2H,C⁸), H 4.13 (d, J (H, H)=5.82, C⁹H)；³¹P{¹H}NMR(121.5MHz, CD₂Cl₂): δ=28.48 (d, J (P, P)=5.83Hz, RuPPh₃), 6.83 (t, J (P, P)=5.83Hz, CPPh₃)；¹³C{¹H} NMR(75.5MHz,CD₂Cl₂,plus ¹³C-dept 135,¹H-¹³C HSQC and ¹H-¹³C HMBC): δ=355.49 (br, C¹), 246.21 (t, J (P, C)=12.93, C⁷), 187.72 (dt, J (P, C)=25.69Hz, J (P, C)=4.87Hz, C⁴), 181.02 (d, J (P, C)=2.03Hz, C⁵), 166.31 (t, J (P, C)=3.95Hz, C⁶), 156.77 (d, J (P, C)= 16.65Hz,C³), 128.38-135.99 (other aromatic carbons), 124.04 (dt, J (P, C)=93.58Hz, J (P, C)= 3.80Hz,C²), 119.56 (aromatic carbons), 71.28 (s, C⁹),69.01(s,C⁸)；HRMS (ESI): m/z theoretical value [C₆₃H₅₁ClOP₃Ru]⁺,1053.1879；Measured value 1053.1894.

Embodiment 3

In above formula, [Ru]¹For RuCl (PPh₃)₂。

In addition to following characteristics, the preparation method of compound I-8 is identical as the preparation method of compound I-1 in embodiment 1:

By HC ≡ CCH (OH) C ≡ CCH used in embodiment 1₂C(COOMe)₂CH₂C ≡ CH changes the preparation of equimolar number into HC ≡ CCPh (OH) C ≡ CCH made from example 4₂C(COOMe)₂CH₂C≡CH。

Red solid compound I-8 is obtained, yield: 70% (mole that the yield of compound I-8 is compound I-8/ RuCl₂(PPh₃)₃Mole × 100%).

¹H NMR(300.1MHz,CD₂Cl₂): δ=13.07 (s, 1H, C⁷), H 6.98-7.82 (51H, phenyl and C³H), 3.65(s,6H,COOCH₃), 2.97 (t, J (H, H)=3.64, C¹⁰H),2.77(s,C⁸H)；³¹P{¹H}NMR(121.5MHz, CD₂Cl₂): δ=29.60 (d, J (P, P)=5.90Hz, RuPPh₃), 6.37 (t, J (P, P)=5.88Hz, CPPh₃)；¹³C{¹H} NMR(75.5MHz,CD₂Cl₂): δ=356.96 (br, C¹), 251.88 (t, J (P, C)=11.97, C⁷),190.22(dt,J(P, C)=25.66Hz, J (P, C)=4.98Hz, C⁴), 180.99 (d, J (P, C)=1.96Hz, C⁵),171.78(s,COOCH₃), 164.56 (t, J (P, C)=4.23Hz, C⁶), 154.98 (dt, J (P, C)=14.45Hz, J (P, C)=3.06Hz, C³), 128.19-135.75 (other aromatic carbons), 122.87 (dt, J (P, C)=92.98Hz, J (P, C)=4.03Hz, C²),119.58 (aromatic carbon), 64.15 (s, C⁹),53.64(s,COOCH₃),39.07(s,C⁸),37.34(s,C¹⁰)；HRMS (ESI): m/z is theoretical It is worth [C₇₄H₆₁ClO₄P₃Ru]⁺,1243.2509；Measured value 1243.2505.

Embodiment 4

In above formula, [Ru]¹For RuCl (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of the compound I-1 in embodiment 1 of compound I-11 It is same:

By HC ≡ CCH (OH) C ≡ CCH used in embodiment 1₂C(COOMe)₂CH₂C ≡ CH changes the preparation of equimolar number into HC ≡ CCH (OH) C ≡ CCH made from example 5₂OCH₂C≡CMe。

Obtain red solid compound I-11, yield: 71% (yield of compound I-11 be compound I-11 mole Amount/RuCl₂(PPh₃)₃Mole × 100%).

¹H NMR(300.1MHz,CD₂Cl₂): δ=7.34 (s, 1H, C³), H 7.00-7.82 (46H, phenyl and C³H),4.35 (s,2H,C⁸), H 4.14 (d, J (H, H)=5.81, C⁹H)；³¹P{¹H}NMR(121.5MHz,CD₂Cl₂): δ=28.47 (d, J (P, P)=5.83Hz, RuPPh₃), 6.82 (t, J (P, P)=5.82Hz, CPPh₃)；¹³C{¹H}NMR(75.5MHz,CD₂Cl₂): δ= 355.48(br,C¹), 246.20 (t, J (P, C)=12.94, C⁷), 187.73 (dt, J (P, C)=25.68Hz, J (P, C)= 4.86Hz,C⁴), 181.00 (d, J (P, C)=2.04Hz, C⁵), 166.30 (t, J (P, C)=3.96Hz, C⁶),156.76(d,J (P, C)=16.64Hz, C³), 128.37-135.98 (other aromatic carbons), 124.03 (dt, J (P, C)=93.57Hz, J (P, C) =3.81Hz, C²), 119.55 (aromatic carbons), 71.27 (s, C⁹),69.00(s,C⁸),23.22(s,CH₃)；HRMS(ESI):m/z Theoretical value [C₆₃H₅₁ClOP₃Ru]⁺,1053.1879；Measured value 1053.1894.

Embodiment 5

In above formula, [Ru]¹For RuCl (PPh₃)₂。

In addition to following characteristics, the preparation method of compound I-5 is identical as the preparation method of compound I-1 in embodiment 1:

Reaction temperature in embodiment 1 is increased to 60 DEG C by room temperature, the time was extended to 1 day by 1 hour.

Red solid compound I-5 is obtained, yield: 62% (mole that the yield of compound I-5 is compound I-5/ RuCl₂(PPh₃)₃Mole × 100%).

¹H NMR(300.1MHz,CD₂Cl₂): δ=12.67 (ddd, J (PH)=18.35Hz, J (PH)=4.98Hz, J (HH)=2.64Hz, 1H, C¹), H 8.26 (dd shows as t, J (PH)=2.64Hz, J (HH)=2.63Hz, 1H, C³H),6.86- 7.78(m,45H,Ph),3.62(s,6H,COOCH₃), 2.94 (t, J (H, H)=3.61, C¹⁰H),2.74(s,C⁸H)；³¹P{¹H} NMR(121.5MHz,CD₂Cl₂): δ=32.54 (d, J (P, P)=4.92Hz, RuPPh₃), 12.17 (t, J (P, P)=4.92Hz, CPPh₃)；¹³C{¹H}NMR(75.5MHz,CD₂Cl₂): δ=345.73 (br, C⁷), 249.97 (br, J (P, C)=12.92, C¹), 193.76(s,C⁵), 187.72 (dt, J (P, C)=22.28Hz, J (P, C)=5.84Hz, C⁴),157.57(s,C⁶),143.62 (d, J (P, C)=22.32Hz, C³), 127.06-134.35 (m, Ph), 126.22 (d, J (P, C)=68.71Hz, C²),117.72 (d, J (P, C)=88.43Hz, Ph), 64.12 (s, C⁹),53.64(s,COOCH₃),39.05(s,C⁸),37.34(s,C¹⁰)； HRMS (ESI): m/z theoretical value [C₆₈H₅₇ClO₄P₃Ru]⁺,1167.2212；Measured value 1167.2216.

Embodiment 6

In above formula, [Ir]²For IrCl (PPh₃)₂, [Ir]¹For Ir (PPh₃)₂。

Under nitrogen atmosphere, under magnetic stirring, by compound II-10 (300mg, 0.25mmol) made from embodiment 9 With Cs₂CO₃Methylene chloride (dosage of methylene chloride the is 15mL) solution of (414mg, 1.25mmol) reacts 1h, solution at room temperature Color is red.The filtrate obtained after reaction solution is filtered is concentrated into 2mL with vacuum pump, then washs (washing three with n-hexane It is secondary, each 50mL) red solid compound I-7 is obtained, yield: 85% (mole that the yield of compound I-7 is compound I-7/ Mole × 100% of compound II-10).

¹H-NMR(300.1MHz,CD₂Cl₂): δ=13.31 (s, 1H, C⁷H),7.60(s,1H,C³H),7.01-7.78(m, 45H,Ph),2.43(m,2H,C¹⁰), H 2.02 (tt shows as quintet, J (HH)=7.26Hz, 2H, C⁹H),1.78ppm(t,J (HH)=7.28Hz, 2H, C⁸H).³¹P{¹H}NMR(121.5MHz,CD₂Cl₂): δ=11.21 (t, J (PP)=5.73Hz, CPPh₃), -3.24ppm (d, J (PP)=5.73Hz, IrPPh₃).¹³C{¹H}NMR(75.5MHz,CD₂Cl₂): δ=341.56 (dt, apparent q, J (PC)=13.34Hz, J (PC)=13.34Hz, C¹), 226.58 (t, J (PC)=10.58Hz, C⁷), 180.45(s,C⁵), 176.50 (t, J (PC)=3.43Hz, C⁶), 173.04 (dt, J (PC)=23.40Hz, J (PC)= 3.31Hz,C⁴), 147.76 (dt, J (PC)=15.35Hz, J (PC)=2.47Hz, C³),128.07-135.45(Ph),127.89 (dt, J (PC)=78.84Hz, J (PC)=5.61Hz, C²), 120.56 (d, J (PC)=70.83Hz, Ph), 33.32 (s, C⁸), 28.57(s,C¹⁰),29.30ppm(s,C⁹) .HRMS (ESI): m/z theoretical value [C₆₃H₅₄P₃Ir]⁺,1096.3062；Measured value, 1096.3058.

Embodiment 7

In above formula, [Rh]²For RhCl (PPh₃)₂, [Rh]¹For Rh (PPh₃)₂。

In addition to following characteristics, the preparation method of compound I-6 is identical as the preparation method of compound I-7 in embodiment 6:

Change compound II-10 used in embodiment 6 into made from the embodiment 11 of equimolar number compound II-2.

Red solid compound I-6 is obtained, yield: 83% (mole that the yield of compound I-6 is compound I-6/ Mole × 100% of compound II-2).

¹H-NMR(300.1MHz,CD₂Cl₂): δ=13.02 (s, 1H, C⁷H),7.68(s,1H,C³H),7.08-7.75(m, 45H,Ph),2.47(m,2H,C¹⁰), H 2.06 (tt shows as quintet, J (HH)=7.29Hz, 2H, C⁹H),1.82ppm(t,J (HH)=7.29Hz, 2H, C⁸H).³¹P{¹H}NMR(121.5MHz,CD₂Cl₂): δ=35.63 (dd, J (RhP)=108.20Hz, J (PP)=5.55Hz, RhPPh₃), 11.02 (d, J (PP)=5.55Hz, CPPh₃)；¹³C{¹H}NMR(75.5MHz,CD₂Cl₂):δ =347.32 (dt shows as quartet, J (PC)=13.02Hz, J (PC)=13.02Hz, C¹), 226.10 (t, J (PC)= 10.58Hz,C⁷),180.00(s,C⁵), 176.30 (t, J (PC)=3.23Hz, C⁶), 173.58 (dt, J (PC)=23.47Hz, J (PC)=3.30Hz, C⁴), 145.47 (dt, J (PC)=15.25Hz, J (PC)=2.35Hz, C³),129.06-134.25(Ph), 127.56 (dt, J (PC)=78.85Hz, J (PC)=5.56Hz, C²), 120.54 (d, J (PC)=70.88Hz, Ph), 34.32 (s,C⁸),26.57(s,C¹⁰),22.30ppm(s,C⁹).HRMS(ESI):m/z calcd for[C₆₄H₅₃P₃Rh]⁺, 1017.2410；found,1017.2406.

Embodiment 8

In above formula, [Rh]²For RhCl (PPh₃)₂, [Rh]¹For Rh (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of the compound I-7 in embodiment 6 of compound I-14 It is same:

Change compound II-10 used in embodiment 6 into made from the embodiment 12 of equimolar number compound II-13.

Obtain red solid compound I-14, yield: 81% (yield of compound I-14 be compound I-14 mole Amount/compound II-13 mole × 100%).

¹H-NMR(300.1MHz,CD₂Cl₂): δ=13.23 (s, 1H, C⁷H),7.85(s,1H,C³H),7.02-7.68(m, 50H,Ph),2.52(m,2H,C¹⁰), H 2.04 (tt shows as quintet, J (HH)=7.18Hz, 2H, C⁹H),1.95ppm(t,J (HH)=7.18Hz, 2H, C⁸H).³¹P{¹H}NMR(121.5MHz,CD₂Cl₂): δ=35.72 (dd, J (RhP)=108.32Hz, J (PP)=5.50Hz, RhPPh₃), 10.95 (d, J (PP)=5.50Hz, CPPh₃)；¹³C{¹H}NMR(75.5MHz,CD₂Cl₂):δ =348.24 (dt shows as quartet, J (PC)=13.22Hz, J (PC)=13.22Hz, C¹), 225.21 (t, J (PC)= 10.37Hz,C⁷),181.25(s,C⁵), 175.36 (t, J (PC)=3.28Hz, C⁶), 173.79 (dt, J (PC)=22.35Hz, J (PC)=3.39Hz, C⁴), 145.57 (dt, J (PC)=15.23Hz, J (PC)=2.33Hz, C³),129.15-134.89(Ph), 126.35 (dt, J (PC)=78.59Hz, J (PC)=5.53Hz, C²), 120.65 (d, J (PC)=71.22Hz, Ph), 34.96 (s,C⁸),29.65(s,C¹⁰),23.63ppm(s,C⁹).HRMS(ESI):m/z calcd for[C₇₀H₅₇P₃Rh]⁺, 1093.2723；found,1093.2718.

Embodiment 9

Preparation method of the present embodiment to metal bridge location fused ring compound shown in formula II.

In above formula, [Ir]²For IrCl (PPh₃)₂, CDCl₃For deuterated chloroform.

In addition to following characteristics, the preparation method and the preparation method phase of the compound I-1 in embodiment 1 of compound II-10 It is same:

By HC ≡ CCH (OH) C ≡ CCH used in embodiment 1₂C(COOMe)₂CH₂C ≡ CH changes the preparation of equimolar number into HC ≡ CCH (OH) C ≡ C (CH made from example 1₂)₃C ≡ CH, changes DCM into CDCl₃(deuterated chloroform), while by RuCl₂(PPh₃)₃ Change IrHCl into₂(PPh₃)₃。

Obtain red solid compound II-10, yield: 35% (yield of compound II-10 is compound II-10 Mole/IrHCl₂(PPh₃)₃Mole × 100%).

¹H-NMR(600.1MHz,CDCl₃): δ=14.34 (s, 1H, C⁷H), 12.66 (d, J (PH)=20.03Hz, 1H, C¹), H 8.67 (t, J (PH)=2.35Hz, 1H, C³H),6.98-7.90(m,45H,Ph),2.56(m,2H,C¹⁰H),1.64(tt, Show as quintet J (HH)=7.44Hz, 2H, C⁹), H 1.15 (t, J (HH)=7.44Hz, 2H, C⁸H)；³¹P{¹H}NMR (242.9MHz,CDCl₃): δ=10.91 (t, J (PP)=5.97Hz, CPPh₃), -5.77 (d, J (PP)=5.97Hz, IrPPh₃)；¹³C{¹H}NMR(150.9MHz,CDCl₃): δ=230.16 (br, C⁷),215.13(br,C¹),186.44(s,C⁵), 184.96(s,C⁶), 169.34 (dt, J (PC)=22.59Hz, J (PC)=2.90Hz, C⁴), 151.98 (d, J (PC)= 24.44Hz,C³), 137.51 (dt, J (PC)=62.94Hz, J (PC)=3.21Hz, C²),119.36-135.16(Ph),31.75 (s,C⁸),31.00(s,C¹⁰),28.75(s,C⁹)；HRMS (ESI): m/z theoretical value [C₆₄H₅₄ClP₃Ir]⁺,1143.2748；It is real Measured value 1143.2739.

Embodiment 10

In above formula, [Rh]²For RhCl (PPh₃)₂, HBF₄·H₂O is tetrafluoroborate solution.

Under nitrogen atmosphere, under magnetic stirring, toward RhCl (PPh₃)₃(1.40g, 1.46mmol) and PPh₃(1.91g, HC ≡ CCH made from preparation example 2 is added dropwise in methylene chloride (dosage of methylene chloride is 40mL) solution 7.3mmol) (OH)C≡CCH₂C(COOMe)₂CH₂The methylene chloride (dosage of methylene chloride is 5mL) of C ≡ CH (0.57g, 2.19mmol) is molten Liquid, reacts 1h at room temperature, and solution colour is red.Rapidly join HBF₄·H₂O (0.33mL, 2.68mmol), solution colour is at once Become red from yellow, reacts 10min again at room temperature, reaction solution is concentrated into 5mL with vacuum pump, is then washed and (washed with n-hexane Wash three times, each 50mL) obtain red solid compound II-1, yield: 92% (yield of compound II-1 be compound The mole of II-1/RhCl (PPh₃)₃Mole × 100%).

¹H-NMR(600.1MHz,CD₂Cl₂): δ=12.83 (s, 1H, C⁷H), 11.76 (d, J (PH)=21.49Hz, 1H, C¹H),6.89-7.82(45H,Ph),7.91(s,1H,C³H),3.64(s,6H,COOCH₃),3.04(s,2H,C¹⁰H),2.33(s, 2H,C⁸H)；³¹P{¹H}NMR(242.9MHz,CD₂Cl₂): δ=26.82 (d, J (RhP)=105.77Hz, RhPPh₃),9.72(s, CPPh₃)；¹³C{¹H}NMR(150.5MHz,CD₂Cl₂): δ=265.29 (br, C⁷),239.66(br,C¹),188.77(s,C⁵), 188.66(br,C⁴),172.54(s,C⁶),171.10(s,COOCH₃), 157.38 (d, J (PC)=25.91Hz, C³), 134.14-135.39 (Ph), 131.86 (dt, J (PC)=55.99Hz, J (PC)=4.31Hz, C²),128.40-131.03 (Ph), 119.19 (d, J (PC)=87.55Hz, Ph), 63.73 (s, C⁹),53.68(s,COOCH₃),39.83(s,C⁸),38.60 (s,C¹⁰)；HRMS (ESI): m/z theoretical value [C₆₈H₅₈ClO₄P₃Rh]⁺,1169.2286[M]⁺；Measured value 1169.2299.

Wherein, compound HC ≡ CCH (OH) C ≡ CCH₂C(COOMe)₂CH₂The preparation method of C ≡ CH is referring to embodiment 1.

Embodiment 11

In addition to following characteristics, the preparation method and the preparation method phase of the compound II-1 in embodiment 10 of compound II-2 It is same:

By HC ≡ CCH (OH) C ≡ CCH used in embodiment 10₂C(COOMe)₂CH₂C ≡ CH changes the system of equimolar number into HC ≡ CCH (OH) C ≡ C (CH made from standby example 1₂)₃C≡CH。

Obtain red solid compound II-2, yield: 89% (yield of compound II-2 be compound II-1 mole Amount/RhCl (PPh₃)₃Mole × 100%).

¹H-NMR(600.1MHz,CD₂Cl₂): δ=13.08 (s, 1H, C⁷H), 11.50 (d, J (PH)=21.48Hz, 1H, C¹H),8.07(s,1H,C³H),6.88-7.80(45H,Ph),2.20(m,2H,C¹⁰), H 1.47 (tt, J (HH)=7.31Hz, J (HH)=7.31Hz, 2H, C⁹), H 1.36ppm (t, J (HH)=7.31Hz, 2H, C⁸H)；³¹P{¹H}NMR(242.9MHz, CD₂Cl₂): δ=28.70 (dd, J (RhP)=108.51Hz, J (PP)=5.87Hz, RhPPh₃), 9.14ppm (d, J (PP)= 5.87Hz,CPPh₃)；¹³C{¹H}NMR(150.5MHz,CD₂Cl₂): δ=261.20 (br, C⁷), 239.86 (dt, J (RhC)= 35.44Hz, J (PC)=10.37Hz, C¹),1195.42(s,C⁵), 187.62 (ddt, J (RhC)=29.21Hz, J (PC)= 25.20Hz, J (PC)=4.83Hz, C⁴),178.70(s,C⁶), 157.32 (d, J (PC)=26.58Hz, C³),130.20- 134.95 (Ph), 129.41 (ddt, J (PC)=58.75Hz, J (RhC)=8.59Hz, J (PC)=4.48Hz, C²),127.80- 128.45 (Ph), 119.00 (d, J (PC)=87.27Hz, Ph), 32.50 (s, C⁸),31.46(s,C⁹),28.42ppm(s, C¹⁰)；HRMS (ESI): m/z theoretical value [C₆₄H₅₅ClP₃Rh]⁺,1053.2176[M]⁺；Measured value 1053.2170.

Embodiment 12

In addition to following characteristics, the preparation method of compound II-13 and the preparation method of the compound II-1 in embodiment 10 It is identical:

By HC ≡ CCH (OH) C ≡ CCH used in embodiment 10₂C(COOMe)₂CH₂C ≡ CH changes the system of equimolar number into HC ≡ CCPh (OH) C ≡ C (CH made from standby example 8₂)₃C≡CH。

Obtain red solid compound II-13, yield: 86% (yield of compound II-13 is compound II-13 Mole/RhCl (PPh₃)₃Mole × 100%).

¹H-NMR(600.1MHz,CD₂Cl₂): δ=11.66 (d, J (PH)=21.25Hz, 1H, C¹H),8.13(s,1H, C³H),6.78-7.89(50H,Ph),2.25(m,2H,C¹⁰H), 1.53 (tt, J (HH)=7.28Hz, J (HH)=7.28Hz, 2H, C⁹), H 1.35ppm (t, J (HH)=7.28Hz, 2H, C⁸H)；³¹P{¹H}NMR(242.9MHz,CD₂Cl₂): δ=28.59 (dd, J (RhP)=108.48Hz, J (PP)=5.85Hz, RhPPh₃), 9.19ppm (d, J (PP)=5.85Hz, CPPh₃)；¹³C{¹H}NMR (150.5MHz,CD₂Cl₂): δ=258.23 (br, C⁷), 237.85 (dt, J (RhC)=35.43Hz, J (PC)=10.34Hz, C¹),193.42(s,C⁵), 185.63 (ddt, J (RhC)=29.11Hz, J (PC)=25.51Hz, J (PC)=4.63Hz, C⁴), 175.63(s,C⁶), 157.96 (d, J (PC)=26.75Hz, C³), 129.65-134.55 (Ph), 128.65 (ddt, J (PC)= 58.55Hz, J (RhC)=8.74Hz, J (PC)=4.63Hz, C²), 127.85-128.43 (Ph), 118.30 (d, J (PC)= 87.25Hz,Ph),32.45(s,C⁸),31.23(s,C⁹),28.21ppm(s,C¹⁰)；HRMS (ESI): m/z theoretical value [C₇₀H₅₈ClP₃Rh]⁺,1129.2489[M]⁺；Measured value 1129.2485.

Embodiment 13

In above formula, [Ir]²For IrCl (PPh₃)₂, HBF₄·H₂O is tetrafluoroborate solution.

In addition to following characteristics, the preparation method of compound II-11 and the preparation method of the compound II-1 in embodiment 10 It is identical:

By the RhCl (PPh in embodiment 10₃)₃Change the IrCl (PPh of equimolar number into₃)₃。

Obtain red solid compound II-11, yield: 55% (yield of compound II-11 is compound II-11 Mole/IrCl (PPh₃)₃Mole × 100%).

¹H-NMR(600.1MHz,CD₂Cl₂): δ=13.97 (s, 1H, C⁷H), 12.90 (d, J (PH)=20.22Hz, 1H, C¹), H 8.40 (dd, J (PH)=2.34Hz, J (HH)=2.34Hz, 1H, C³H),6.90-7.79(45H,Ph),3.61(s,6H, COOCH₃), 3.32 (t, J (HH)=3.25Hz, 2H, C¹⁰H),1.91ppm(s,2H,C⁸H)；³¹P{¹H}NMR(242.9MHz, CD₂Cl₂): δ=11.05 (s, CPPh₃),-7.59ppm(s,IrPPh₃)；¹³C{¹H}NMR(150.5MHz,CD₂Cl₂): δ= 232.46(br,C⁷),213.38(br,C¹),178.81(s,C⁵),178.48(s,C⁶),170.54(s,C⁶),171.10(s, COOCH₃), 169.21 (d, J (PC)=22.17Hz, C⁴), 151.03 (d, J (PC)=23.94Hz, C³),139.09(dt,J (PC)=62.35Hz, J (PC)=3.44Hz, C²), 127.16-134.29 (Ph), 118.90 (d, J (PC)=87.37Hz, Ph),63.22(s,C⁹),52.65(s,COOCH₃),38.293(s,C⁸),37.29ppm(s,C¹⁰)；HRMS (ESI): m/z is theoretical It is worth [C₆₈H₅₈ClO₄P₃Ir]⁺,1259.2860[M]⁺；Measured value 1259.2864.

Embodiment 14

In addition to following characteristics, the preparation method of compound II-21 and the preparation method of the compound II-1 in embodiment 10 It is identical:

By the RhCl (PPh in embodiment 10₃)₃Change the IrCl (PPh of equimolar number into₃)₃.It will be used in embodiment 10 HC≡CCH(OH)C≡CCH₂C(COOMe)₂CH₂C ≡ CH changes HC ≡ CCH (OH) C ≡ C made from the preparation example 9 of equimolar number into (CH₂)₅C≡CH。

Obtain red solid compound II-21, yield: 53% (yield of compound II-21 is compound II-21 Mole/IrCl (PPh₃)₃Mole × 100%).

¹H-NMR(600.1MHz,CD₂Cl₂): δ=14.02 (s, 1H, C⁷H), 12.95 (d, J (PH)=19.22Hz, 1H, C¹), H 8.35 (dd, J (PH)=2.32Hz, J (HH)=2.10Hz, 1H, C³H),6.95-7.71(45H,Ph),2.25(m,2H, C¹²H),1.53(m,2H,C¹¹H),1.43(m,2H,C¹⁰H),1.40(m,2H,C⁹), H 1.35ppm (t, J (HH)=7.26Hz, 2H,C⁸H)；³¹P{¹H}NMR(242.9MHz,CD₂Cl₂): δ=11.15 (s, CPPh₃),-7.35ppm(s,IrPPh₃)；¹³C{¹H} NMR(150.5MHz,CD₂Cl₂): δ=230.43 (br, C⁷),212.25(br,C¹),177.32(s,C⁵),176.23(s,C⁶), 171.53(s,C⁶),171.12(s,COOCH₃), 169.42 (d, J (PC)=22.16Hz, C⁴), 151.42 (d, J (PC)= 23.97Hz,C³), 136.16 (dt, J (PC)=72.37Hz, J (PC)=3.45Hz, C²),126.32-133.98(Ph), 117.62 (d, J (PC)=87.25Hz, Ph), 33.50 (s, C¹²),35.61(s,C⁸),32.16(s,C¹⁰),28.54(s,C¹¹), 27.52ppm(s,C⁹)；HRMS (ESI): m/z theoretical value [C₆₆H₅₈ClP₃Ir]⁺,1171.3064[M]⁺；Measured value 1171.3058.

Embodiment 15

In above formula, [Ru]¹For RuCl (PPh₃)₂, [Ru]²For RuCO (PPh₃)₂。

Under CO atmosphere, under magnetic stirring, by compound I-1 (300mg, 0.25mmol) and benzene made from embodiment 1 Thiophenol sodium (99mg, 0.75mmol) mixing, is added methylene chloride (20mL), reacts 10min at room temperature, obtain red suspension.It will After suspension is filtered with sand core funnel, filtrate is drained with vacuum pump, crosses neutral alumina column (methylene chloride/methanol=40/1 Volume ratio), be spin-dried for obtaining 264mg red solid compound II-6, yield: 81% (yield of compound II-6 be compound II- 6 mole/compound II-1 mole × 100%).

¹H NMR(500.2MHz,CD₂Cl₂): δ=10.88 (s, 1H, C⁷H), 7.84 (d, J (P, H)=5.45Hz, 1H, C³), H 5.99-7.69 (50H, other fragrance hydrogen), 3.54 (s, 6H, COOCH₃),2.57(s,C¹⁰H),2.11(s,C⁸H)；³¹P {¹H}NMR(202.5MHz,CD₂Cl₂): δ=36.84 (s, RuPPh₃),7.28(s,CPPh₃)；¹³C{¹H}NMR(125.8MHz, CD₂Cl₂,plus ¹³C-dept 135,¹H-¹³C HSQC and ¹H-¹³C HMBC): δ=249.56 (br, C¹),238.51(t,J (P, C)=18.01, C⁷), 203.96 (t, J (P, C)=15.06Hz, RuCO), 197.79 (dt, J (P, C)=27.45Hz, J (P, C)=7.71Hz, C⁴),180.95(s,C⁵),171.71(s,COOCH₃),169.85(s,C⁶), 161.86 (d, J (P, C)= 24.53Hz,C³), 122.00-138.99 (other aromatic carbons), 121.97 (d, J (P, C)=58.68Hz, C²),64.08(s, C⁹),53.32(s,COOCH₃),38.38(s,C¹⁰),37.62(s,C⁸)；HRMS (ESI): m/z theoretical value [C75H62O5P3RuS ]⁺,1269.2569；Measured value 1269.6588.

Embodiment 16

In above formula, [Ru]¹For RuCl (PPh₃)₂, [Ru]²For RuCO (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of the compound II-6 in embodiment 14 of compound II-7 It is same:

The compound I-1 in embodiment 14 is changed into made from the embodiment 3 of equimolar number compound I-8, by benzenethiol Sodium changes the sodium methyl mercaptide of equimolar number into.

Obtain red solid compound II-7, yield: 85% (yield of compound II-7 be compound II-7 mole Amount/compound I-8 mole × 100%).

¹H-NMR(500.2MHz,CD₂Cl₂): δ=10.85 (s, 1H, C⁷H), 7.81 (d, J (PH)=5.35Hz, 1H, C³H),5.96-7.56(50H,Ph),3.52(s,6H,COOCH₃),2.55(s,C¹⁰H),2.45(s,SCH₃),2.10ppm(s, C⁸H)；³¹P{¹H}NMR(202.5MHz,CD₂Cl₂): δ=36.92 (s, RuPPh₃),7.35(s,CPPh₃)；¹³C{¹H}NMR (125.8MHz,CD₂Cl₂): δ=244.32 (br, C¹), 236.52 (t, J (P, C)=18.21, C⁷),203.85(t,J(P,C) =15.11Hz, RuCO), 195.32 (dt, J (P, C)=27.21Hz, J (P, C)=7.65Hz, C⁴),178.65(s,C⁵), 171.31(s,COOCH₃),169.64(s,C⁶), 160.63 (d, J (P, C)=24.32Hz, C³),122.11-138.34(Ph), 121.63 (d, J (P, C)=58.59Hz, C²),64.95(s,C⁹),54.32(s,COOCH₃),38.65(s,C¹⁰),37.52(s, C⁸),14.63(s,SCH₃)；HRMS (ESI): m/z theoretical value [C₇₆H₆₄O₅P₃RuS]⁺,1283.2725；Measured value 1283.2720.

Embodiment 17

In above formula, [Ru]¹For RuCl (PPh₃)₂, [Ru]²For RuCO (PPh₃)₂, Bu₄N⁺Cl^-For tetrabutylammonium chloride.

Under nitrogen atmosphere, in ice bath, toward the dichloromethane of compound I-3 (500mg, 0.46mmol) made from embodiment 2 It is added dropwise dichloroacetic acid (56 μ L, 0.69mmol) in alkane (dosage of methylene chloride is 30mL) solution, after reacting 20min, uses Vacuum pump drains reaction solution, is added tetrabutylammonium chloride (555mg, 0.72mmol), then reaction flask is replaced as CO atmosphere, Methylene chloride is added, reacts 1h at room temperature, reaction solution is red, and reaction solution is concentrated into 5mL with vacuum pump, is then washed with n-hexane It washs and (washs three times, each 50mL), after neutral alumina column (methylene chloride/methanol=40/1 volume ratio), be spin-dried for obtaining 385mg Red solid compound II-9, yield: 75% (yield of compound II-9 be compound II-9 mole/compound II- 3 mole × 100%).

¹H NMR(500.2MHz,CD₂Cl₂): δ=11.80 (d, J (P, H)=20.78Hz, 1H, C¹H),8.18(s,1H, C³H),6.81-7.80(45H,Ph),3.89(s,1H,C⁸H),3.75(s,C⁹H)；³¹P{¹H}NMR(202.5MHz,CD₂Cl₂):δ =41.36 (s, RuPPh₃),10.29(s,CPPh₃)；¹³C{¹H}NMR(125.8MHz,CD₂Cl₂): δ=250.82 (br, C⁷), 244.05(br,C¹), 203.46 (t, J (P, C)=13.44Hz, CO), 198.60 (dt, J (P, C)=27.91Hz, J (P, C)= 7.29Hz,C⁴),180.72(s,C⁵),175.75(s,C⁶), 151.20 (d, J (P, C)=25.55Hz, C³),128.38- 135.58 (Ph), 128.41 (d, J (P, C)=77.20Hz, C²), 120.70 (d, J (P, C)=87.40Hz, Ph), 72.76 (s, C⁹),69.95(s,C⁸)；HRMS (ESI): m/z theoretical value [C₆₄H₅₁O₂ClP₃Ru]⁺,1081.1828；Measured value 1081.1822.

Embodiment 18

Preparation method of the present embodiment to metal bridge location fused ring compound shown in formula III.

In above formula, [Ru]¹For RuCl (PPh₃)₂。

In addition to following characteristics, the preparation method of compound III-1 is identical as the preparation method of compound I-1 in embodiment 1:

By HC ≡ CHC (OH) C ≡ CCH used in embodiment 1₂C(COOMe)₂CH₂C ≡ CH changes the preparation of equimolar number into HC ≡ CCH (OH) C ≡ CCH made from example 10₂OCH₂CH=C=CH.

Obtain red solid compound III-1, yield: 61% (yield of compound III-1 is compound III-1 Mole/RuCl₂(PPh₃)₃Mole × 100%).

¹H NMR(300.1MHz,CD₂Cl₂): δ=13.92 (d, J (P, H)=17.35,1H, C¹H),7.74(s,1H, C³), H 6.89-7.83 (46H, fragrant hydrogen and C³H),3.72(s,6H,COOCH₃),3.68(s,2H,C⁸H),3.08(s,C¹¹H), 2.39(s,C⁹H)；³¹P{¹H}NMR(121.5MHz,CD₂Cl₂): δ=21.70 (d, J (P, P)=4.23Hz, RuPPh₃),9.87 (t, J (P, P)=4.23Hz, CPPh₃)；¹³C{¹H}NMR(75.5MHz,CD₂Cl₂,plus ¹³C-dept 135,¹H-¹³C HSQC and ¹H-¹³C HMBC): δ=269.25 (br, C¹), 250.37 (t, J (P, C)=4.80Hz, C⁷),202.22(dt,J(P,C) =26.68Hz, J (P, C)=5.74Hz, C⁴),194.25(s,C⁵),171.09(s,COOCH₃),153.55(s,C⁶),149.87 (d, J (P, C)=23.14Hz, C³), 129.82 (dt, J (P, C)=66.67Hz, J (P, C)=3.68Hz, C²),127.64- 135.44 (Ph and C²), 119.51 (d, J (P, C)=88.14Hz, Ph), 65.37 (s, C¹⁰),53.78(s,COOCH₃),45.64 (s,C⁸),39.10(s,C⁹),34.93(s,C¹¹)；HRMS (ESI): m/z theoretical value [C₆₈H₅₇ClO₄P₃Ru]⁺1216.2047 real Measured value 1216.2041.

Embodiment 19

In above formula, [Ru]¹For RuCl (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of compound I-1 in embodiment 1 of compound III-20 It is same:

By HC ≡ CHC (OH) C ≡ CCH used in embodiment 1₂C(COOMe)₂CH₂C ≡ CH changes the preparation of equimolar number into HC ≡ CCH (OH) C ≡ CCH made from example 11₂OCH₂CH=C=CPh.

Obtain brown solid compound III-20, yield: 64% (yield of compound III-20 be compound III-20 Mole/RuCl₂(PPh₃)₃Mole × 100%).

¹H NMR(300.1MHz,CD₂Cl₂): δ=13.81 (d, J (P, H)=17.24,1H, C¹H),7.63(s,1H, C³), H 6.78-7.72 (51H, fragrant hydrogen and C³H),3.61(s,6H,COOCH₃),3.57(s,1H,C⁸H),3.19(s,C¹¹H), 2.50(s,C⁹H)；³¹P{¹H}NMR(121.5MHz,CD₂Cl₂): δ=21.81 (d, J (P, P)=4.34Hz, RuPPh₃), 9.76ppm (t, J (P, P)=4.34Hz, CPPh₃)；¹³C{¹H}NMR(75.5MHz,CD₂Cl₂): δ=269.14 (br, C¹), 250.26 (t, J (P, C)=4.71Hz, C⁷), 202.11 (dt, J (P, C)=26.57Hz, J (P, C)=5.85Hz, C⁴), 194.14(s,C⁵),171.44(s,COOCH₃),153.22(s,C⁶), 149.75 (d, J (P, C)=23.12Hz, C³),129.71 (dt, J (P, C)=66.56Hz, J (P, C)=3.57Hz, C²), 127.43-135.55 (Ph and C²), 119.40 (d, J (P, C)= 88.03Hz,Ph),65.26(s,C¹⁰),53.67(s,COOCH₃),45.53(s,C⁸),39.02(s,C⁹),34.75(s,C¹¹)； HRMS (ESI): m/z theoretical value [C₇₄H₆₁ClO₄P₃Ru]⁺1243.2509, measured value 1243.2508.

Embodiment 20

In above formula, [Ru]¹For RuCl (PPh₃)₂。

Under the conditions of dichloroacetic acid (22 μ L, 0.28mmol) is existing, under nitrogen atmosphere, in ice bath, made toward embodiment 1 Cyclohexyl is added in methylene chloride (dosage of methylene chloride is 20mL) solution of the compound I-1 (553mg, 0.46mmol) obtained Isocyanide (571 μ L, 4.6mmol) (purchased from resistance to Jilin Chemical is pacified), reacts 1.5h at room temperature, and reaction solution becomes green, reaction from red Liquid is concentrated into 5mL with vacuum pump, after silicagel column (100-200 mesh, methylene chloride/methanol=20/1), is spin-dried for obtaining 129mg green Solid-like compound III-6, yield: 72% (yield of compound III-6 be compound III-6 mole/compound I-1 Mole × 100%).

¹H NMR(300.1MHz,CD₂Cl₂): δ=13.01 (d, J (P, H)=17.02,1H, C¹H),7.41(s,1H, C³), H 6.56-7.50 (46H, fragrant hydrogen and C³H),3.67(s,6H,COOCH₃),3.55(s,1H,C⁸H),3.32(s,C¹¹H), 3.08(m,1H,Cy),2.74(s,C⁹H),2.15(m,4H,Cy),1.63(m,4H,Cy),1.50(m,2H,Cy)；³¹P{¹H}NMR (121.5MHz,CD₂Cl₂): δ=30.75 (s, RuPPh₃),8.59ppm(s,CPPh₃)；¹³C{¹H}NMR(75.5MHz, CD₂Cl₂): δ=267.26 (br, C¹), 251.35 (t, J (P, C)=4.61Hz, C⁷), 203.46 (dt, J (P, C)= 26.31Hz, J (P, C)=5.63Hz, C⁴),193.16(s,C⁵),174.43(s,COOCH₃),160.34(s,C⁸),156.12 (s,C⁶), 149.75 (d, J (P, C)=23.12Hz, C³), 128.13 (dt, J (P, C)=66.65Hz, J (P, C)=3.65Hz, C²), 126.43-135.13 (Ph and C²), 119.64 (d, J (P, C)=88.21Hz, Ph), 68.32 (s, Cy), 65.64 (s, C¹⁰),53.32(s,COOCH₃),39.74(s,C⁹),34.85(s,C¹¹),25.89(s,Cy),25.36(s,Cy),24.21(s, Cy)；HRMS (ESI): m/z theoretical value [C₇₅H₆₈ClNO₄P₃Ru]⁺1276.3088, measured value 1276.3085.

Embodiment 21

In above formula, [Ru]¹For RuCl (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of compound III-6 in embodiment 20 of compound III-8 It is same:

Cyclohexyl isocyanide used in embodiment 20 is changed into the water of equimolar number.

Obtain red solid compound III-8, yield: 90% (yield of compound III-8 is compound III-8 Mole/compound I-1 mole × 100%).

¹H NMR(600.1MHz,CD₂Cl₂): δ=12.45 (ddd, J (P, H)=13.01Hz, J (P, H)=4.12Hz, J (P, H)=3.74Hz, J (P, H)=2.09Hz, 1H, C¹H),6.85(1H,C³H,determined by ¹H-¹³C HSQC and¹H-¹³C HMBC),6.84-7.81(46H,Ph and C³H mentioned above),3.67(s,6H,COOCH₃),2.81 (s,C⁸H),2.48ppm(s,C¹⁰H)；³¹P{¹H}NMR(242.9MHz,CD₂Cl₂): δ=24.42 (s, RuPPh₃),8.60ppm (s,CPPh₃)；¹³C{¹H}NMR(150.9MHz,CD₂Cl₂): δ=244.24 (br, C⁷), 230.85 (t, J (P, C)=6.38Hz, C¹), 193.06 (dt, J (P, C)=24.67Hz, J (P, C)=6.59Hz, C⁴),192.80(s,C⁵),170.44(s, COOCH₃), 138.22 (dd, J (P, C)=18.73Hz, J (P, C)=7.25Hz, C³),134.08-135.64(Ph),134.01 (s,C⁶), 128.54-130.98 (Ph), 120.86 (d, J (P, C)=82.02Hz, C²), 119.27 (d, J (P, C)= 89.95Hz,Ph),65.30(s,C⁹),54.00(s,COOCH₃), 37.16 (t, J (P, C)=20.17Hz, C¹⁰),31.54ppm (t, J (P, C)=18.48Hz, C⁸)；HRMS (ESI): m/z theoretical value [C₆₈H₅₇ClO₅P₃Ru]⁺1183.2145 measured value 1183.2141.

Embodiment 22

In above formula, [Ru]¹For RuCl (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of compound III-6 in embodiment 20 of compound III-9 It is same:

Cyclohexyl isocyanide used in embodiment 20 is changed into the S of equimolar number₈(purchased from resistance to Jilin Chemical is pacified).

Obtain red solid compound III-9, yield: 90% (yield of compound III-9 is compound III-9 Mole/compound I-1 mole × 100%).

¹H NMR(600.1MHz,CD₂Cl₂): δ=12.44 (ddd, J (P, H)=13.56Hz, J (PH)=4.36Hz, J (P, H)=3.63Hz, J (P, H)=2.22Hz, 1H, C¹H),6.85(s,1H,C³), H 6.73-7.92 (46H, Ph and C³H), 3.78(s,6H,COOCH₃),2.92(s,C⁸H),2.59ppm(s,C¹⁰H)；³¹P{¹H}NMR(242.9MHz,CD₂Cl₂): δ= 24.31(s,RuPPh₃),8.49ppm(s,CPPh₃)；¹³C{¹H}NMR(150.9MHz,CD₂Cl₂): δ=243.13 (br, C⁷), 231.96 (t, J (P, C)=6.27Hz, C¹), 193.17 (dt, J (P, C)=24.56Hz, J (P, C)=6.48Hz, C⁴), 192.69(s,C⁵),170.33(s,COOCH₃), 138.33 (dd, J (P, C)=18.62Hz, J (P, C)=7.14Hz, C³), 134.19-135.75(Ph),134.12(s,C⁶), 128.65-130.87 (Ph), 120.97 (d, J (P, C)=82.91Hz, C²), 119.15 (d, J (P, C)=89.84Hz, Ph), 65.19 (s, C⁹),54.23(s,COOCH₃), 37.56 (t, J (P, C)= 20.17Hz,C¹⁰), 31.66ppm (t, J (P, C)=18.59Hz, C⁸)；HRMS (ESI): m/z theoretical value [C₆₈H₅₇ClSO₄P₃Ru ]⁺1199.1917, measured value 1199.1916.

Embodiment 23

In above formula, [Ir]¹For Ir (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of compound II-1 in embodiment 10 of compound III-10 It is same:

By the RhCl (PPh in embodiment 10₃)₃Change the IrCl (PPh of equimolar number into₃)₃.It will be used in embodiment 10 HC≡CCH(OH)C≡CCH₂C(COOMe)₂CH₂C ≡ CH changes HC ≡ CCH (OH) C ≡ made from the preparation example 6 of equimolar number into CCH₂OCH₂C=C=CH.

Obtain brown solid compound III-10, yield: 41% (yield of compound III-10 be compound III-10 Mole/IrCl (PPh₃)₃Mole × 100%).

¹H-NMR(500.2MHz,CD₂Cl₂): δ=14.23 (d, J (PH)=17.39Hz, 1H, C¹H),8.43(s,1H, C³H),6.90-7.92(m,45H,Ph),4.34(s,2H,C⁹H),3.43(s,2H,C¹⁰H),3.25ppm(s,2H,C⁸H)；³¹P {¹H}NMR(202.5MHz,CD₂Cl₂): δ=11.92 (d, J (PP)=4.95Hz, CPPh₃), -13.39ppm (d, J (PP)= 4.96Hz,IrPPh₃)；¹³C{¹H}NMR(125.8MHz,CD₂Cl₂): δ=239.39 (br, C¹), 226.38 (t, J (PC)= 4.59Hz,C⁷),183.68(s,C⁵), 176.22 (d, J (PC)=25.42Hz, C⁴),163.34(s,C⁶),145.63(d,J (PC)=21.85Hz, C³), 134.88 (dt, J (PC)=70.95Hz, J (PC)=3.96Hz, C²),118.68-134.39 (Ph),69.96(s,C¹⁰),65.63(s,C⁹),23.30ppm(s,C⁸) .HRMS (ESI): m/z theoretical value [C₆₄H₅₃OP₃Ir]⁺ 1123.2933, measured value 1123.2930.

Embodiment 24

In above formula, [Rh]¹For Rh (PPh₃)₂。

In addition to following characteristics, the preparation method of compound III-10 in the preparation method and embodiment 23 of compound III-11 It is identical:

By IrCl (PPh used in embodiment 23₃)₃Change the RhCl (PPh of equimolar number into₃)₃。

Obtain brown solid compound III-11, yield: 75% (yield of compound III-11 be compound III-11 Mole/IrCl (PPh₃)₃Mole × 100%).

¹H-NMR(500.2MHz,CD₂Cl₂): δ=13.44 (d, J (PH)=18.36Hz, 1H, C¹H),8.10(s,1H, C³H),6.79-7.83(m,45H,Ph),4.36(s,2H,C⁹H),3.76(s,2H,C¹⁰H),2.98ppm(s,2H,C⁸H)；³¹P {¹H}NMR(202.5MHz,CD₂Cl₂): δ=30.65 (d, J (PP)=108.36Hz, RhPPh₃),10.32ppm(CPPh₃)；¹³C {¹H}NMR(125.8MHz,CD₂Cl₂): δ=239.65 (br, C¹), 229.34 (t, J (PC)=4.63Hz, C⁷),184.96(s, C⁵), 173.21 (d, J (PC)=25.62Hz, C⁴),164.65(s,C⁶), 145.94 (d, J (PC)=21.87Hz, C³), 133.21 (dt, J (PC)=70.79Hz, J (PC)=3.12Hz, C²),118.32-134.23(Ph),68.41(s,C¹⁰), 64.14(s,C⁹),23.49ppm(s,C⁸) .HRMS (ESI): m/z theoretical value [C₆₄H₅₃OP₃Rh]⁺1033.2359 measured value 1033.2358.

Embodiment 25

In above formula, [Rh]¹For Rh (PPh₃)₂。

In addition to following characteristics, the preparation method of compound III-6 in the preparation method and embodiment 20 of compound III-14 It is identical:

Cyclohexyl isocyanide used in embodiment 20 is changed into the selenium powder of equimolar number (purchased from resistance to Jilin Chemical is pacified)；By Formulas I- 1 compound represented changes -6 compound represented of Formulas I made from embodiment 7 into.

Obtain red solid compound III-14, yield: 90% (yield of compound III-14 be compound III-14 Mole/compound I-6 mole × 100%).

¹H-NMR(400.1MHz,CDCl₃): δ=13.6 (d, J (PH)=14.2Hz, 1H, C¹H),8.3(s,1H,C³H), 7.8–6.8ppm(m,45H,Ph),2.57(m,2H,C¹⁰), H 1.65 (tt, J (HH)=7.44Hz, 2H, C⁹H),1.16(t,J (HH)=7.44Hz, 2H, C⁸H).³¹P-NMR(162.0MHz,CDCl₃): δ=12.2 (s, CPPh₃),–8.5ppm(s, OsPPh₃).¹³C-NMR(100.6MHz,CDCl₃): δ=252.8 (t, J (PC)=6.1Hz, C⁷),241.7(br,C¹),183.2 (dt, J (PC)=21.7Hz, J (PC)=4.4Hz, C⁴),166.3(s,C⁵), 153.7 (d, J (PC)=20.1Hz, C³),149.4 (s,C⁶), 128.7 (d, J (PC)=81.8Hz, C2), 135.5-117.7ppm (m, Ph and C2), 31.77 (s, C⁸),31.22(s, C¹⁰),28.76(s,C⁹) .HRMS (ESI): m/z theoretical value [C₆₄H₅₃SeP₃Rh]⁺1097.1575, measured value 1097.1573.

Embodiment 26

Preparation method of the present embodiment to metal bridge location fused ring compound shown in formula IV.

In above formula, [Ru]¹For RuCl (PPh₃)₂。

Under dichloroacetic acid (22 μ L, 0.28mmol) existence condition, under nitrogen atmosphere, in ice bath, it is made toward embodiment 2 Compound I-3 (500mg, 0.46mmol) methylene chloride (dosage of methylene chloride be 10mL) solution in ethoxy is added dropwise Ethyl-acetylene (hexane solution that 178 μ L mass fractions are 50% contains ethoxyacetylene 0.90mmol), reacts 1.5h at room temperature, Reaction solution becomes green from red, and reaction solution is concentrated into 5mL with vacuum pump, after silicagel column (100-200 mesh, methylene chloride/first Alcohol=20/1 volume ratio), be spin-dried for obtaining 129mg green solid compound IV-1, yield: 62% (yield of compound IV-1 is The mole of compound IV-1/compound I-3 mole × 100%).

The spectral data of metal bridge location fused ring compound IV-1 obtained is as follows:

¹H NMR(300.1MHz,CD₂Cl₂): δ=12.40 (dd, J (P, H)=18.71Hz, J (P, H)=4.23Hz 1H, C¹H),6.88-7.77(45H,Ph),6.16(br,1H,C³), H 5.85 (t, J (P, H)=2.11Hz, 1H, C⁸H),3.68(q,J (H, H)=7.11Hz, OCH₂CH₃),3.52(s,C¹⁰H),3.43(s,C¹¹), H 1.23 (t, J (H, H)=7.11Hz, OCH₂CH₃) ；³¹P{¹H}NMR(121.5MHz,CD₂Cl₂): δ=19.84 (d, J (P, P)=2.83Hz, RuPPh₃), 6.45 (t, J (P, P)= 2.83Hz,CPPh₃)；¹³C{¹H}NMR(75.5MHz,CD₂Cl₂): δ=253.15 (br, C¹),212.11(br,C⁹),204.92 (t, J (P, C)=8.92Hz, C⁷), 191.02 (dt, J (P, C)=28.00Hz, J (P, C)=9.16Hz, C⁴),188.04(s, C⁵),151.34(s,C⁶), 147.14 (d, J (P, C)=24.94Hz, C³),126.77-133.90(Ph),125.87(t,J(P, C)=3.73Hz, C⁸), 121.36 (d, J (P, C)=71.91Hz, C²), 118.69 (d, J (P, C)=88.44Hz, Ph), 68.74 (s,C¹¹),68.23(s,OCH₂CH₃),65.11(s,C¹⁰),12.96(s,OCH₂CH₃)；HRMS (ESI): m/z theoretical value [C₆₇H₅₇ClO₂P₃Ru]⁺,1123.2298；Measured value 1123.2327.

Embodiment 27

In above formula, [Ru]¹For RuCl (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of compound IV-1 in embodiment 26 of compound IV-5 It is same:

Change ethoxyacetylene used in embodiment 26 into equimolar number(purchased from resistance to Jilin Chemical is pacified).

Obtain green solid compound IV-5, yield: 60% (yield of compound IV-5 be compound IV-5 mole Amount/compound I-6 mole × 100%).

The spectral data of metal bridge location fused ring compound IV-5 obtained is as follows:

¹H NMR(300.1MHz,CD₂Cl₂): δ=12.35 (dd, J (P, H)=18.56Hz, J (P, H)=4.18Hz 1H, C¹H),6.83-7.72(50H,Ph),6.11(br,1H,C³H),2.5(s,COCH₃),3.52(s,C¹⁰H),3.43(s,C¹¹H), ；³¹P{¹H}NMR(121.5MHz,CD₂Cl₂): δ=19.79 (d, J (P, P)=2.78Hz, RuPPh₃), 6.40 (t, J (P, P)= 2.88Hz,CPPh₃)；¹³C{¹H}NMR(75.5MHz,CD₂Cl₂): δ=254.10 (br, C¹),213.06(br,C⁹),203.87 (t, J (P, C)=8.87Hz, C⁷), 190.07 (dt, J (P, C)=28.15Hz, J (P, C)=9.11Hz, C⁴),183.55(s, COCH₃),181.09(s,C⁵),150.29(s,C⁶), 146.09 (d, J (P, C)=24.89Hz, C³),126.72-133.85 (Ph), 125.82 (t, J (P, C)=3.68Hz, C⁸), 121.31 (d, J (P, C)=70.86Hz, C²),118.64(d,J(P,C) =88.39Hz, Ph), 70.23 (s, C¹¹),68.06(s,C¹⁰)；31.64(s,COCH₃)；HRMS (ESI): m/z theoretical value [C₇₃H₆₁ClO₂P₃Ru]⁺,1199.2611；Measured value 1199.2604.

Embodiment 28

In above formula, [Rh]¹For Rh (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of compound IV-1 in embodiment 26 of compound IV-8 It is same:

Change compound I-3 used in embodiment 26 into made from the embodiment 7 of equimolar number compound I-6.

Obtain green solid compound IV-8, yield: 60% (yield of compound IV-8 be compound IV-8 mole Amount/compound I-6 mole × 100%).

The spectral data of metal bridge location fused ring compound IV-8 obtained is as follows:

¹H NMR(300.1MHz,CD₂Cl₂): δ=12.17 (dd, J (P, H)=19.40Hz, J (P, H)=3.73Hz 1H, C¹H),7.88(s,1H,C³), H 6.88-7.76 (45H, Ph), 3.45 (q, J (H, H)=7.24Hz, OCH₂CH₃),2.45(m, 2H,C¹²), H 2.05 (tt shows as quintet, J (HH)=7.28Hz, 2H, C¹¹), H 1.81ppm (t, J (HH)=7.28Hz, 2H,C¹⁰), H 1.12 (t, J (H, H)=7.24Hz, OCH₂CH₃)；³¹P{¹H}NMR(121.5MHz,CD₂Cl₂): δ=23.59 (d, J (RhP)=103.22Hz, RhPPh₃),7.93(s,CPPh₃)；¹³C{¹H}NMR(75.5MHz,CD₂Cl₂): δ=252.27 (br, C¹),214.80(br,C⁹), 207.46 (t, J (P, C)=8.31Hz, C⁷), 196.20 (dt, J (P, C)=28.05Hz, J (P, C) =9.02Hz, C⁴),188.28(s,C⁵),171.21(s,COOCH₃),151.68(s,C⁶), 146.91 (d, J (P, C)= 24.85Hz,C³), 127.83-135.10 (Ph), 127.10 (t, J (P, C)=3.68Hz, C⁸), 122.86 (d, J (P, C)= 70.71Hz,C²), 120.11 (d, J (P, C)=87.91Hz, Ph), 69.33 (s, OCH₂CH₃),34.21(s,C¹⁰),26.74(s, C¹²),22.21ppm(s,C¹¹),13.88(s,OCH₂CH₃).

Embodiment 29

In above formula, [Rh]¹For Rh (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of compound IV-1 in embodiment 26 of compound IV-12 It is same:

Compound I-3 used in embodiment 26 is changed into made from the embodiment 6 of equimolar number compound I-7, by second Oxygroup acetylene changes equimolar number into

Obtain green solid compound IV-12, yield: 59% (yield of compound IV-12 is compound IV-12 Mole/compound I-7 mole × 100%).

The spectral data of metal bridge location fused ring compound IV-12 obtained is as follows:

¹H NMR(300.1MHz,CD₂Cl₂): δ=12.76 (dd, J (P, H)=18.32Hz, J (P, H)=2.53Hz 1H, C¹H),6.86-7.81(50H,Ph),6.53(s,1H,C³), H 3.54 (q, J (H, H)=7.08Hz, OCH₂CH₃),2.52(m, 2H,C¹²), H 2.11 (tt shows as quintet, J (HH)=7.08Hz, 2H, C¹¹), H 1.79ppm (t, J (HH)=7.28Hz, 2H,C¹⁰), H 1.23 (t, J (H, H)=7.24Hz, OCH₂CH₃)；³¹P{¹H}NMR(121.5MHz,CD₂Cl₂): δ=11.32 (s, CPPh₃),-7.93(s,IrPPh₃).

Embodiment 30

Preparation method of the present embodiment to metal bridge location fused ring compound shown in formula V.

In above formula, [Ru]¹For RuCl (PPh₃)₂, [Ru]³For Ru (PPh₃)₂。

Under nitrogen atmosphere, toward the methylene chloride (dichloro of compound III-1 (300mg, 0.25mmol) made from embodiment 18 Butine ketone is added after stirring 5min to be added silver trifluoromethanesulfonate (128mg, 0.50mmol) in 15mL) solution in the dosage of methane (117 μ L, 1.5mmol), at room temperature react 30min after green solution, filter, be concentrated into 2mL, then be added 30mL ether or The sediment of acquisition is filtered, washed, pillar layer separation (eluant, eluent are as follows: methylene chloride/acetone by n-hexane as precipitating reagent =8/1 volume ratio), be spin-dried for obtaining 187mg compound V-1, yield: 55% (yield of compound V-1 be compound V-1 mole Amount/compound III-1 mole × 100%).

The spectral data of metal bridge location fused ring compound V-1 obtained is as follows:

¹H NMR(600.1MHz,CDCl₃): δ=11.45 (d, J (P, H)=21.21,1H, C¹H),7.65(s,1H, C⁹), H 6.90-7.81 (46H, Ph and C⁹), H 6.39 (d, J (P, H)=4.44,1H, C³H),5.91(s,1H,C⁸H),3.81(s, 6H,COOCH₃),2.97(s,4H,C¹³H and C¹⁵H),1.28(s,3H,C¹²H)；³¹P{¹H}NMR(242.9MHz,CDCl₃):δ =31.04 (s, RuPPh₃),9.28(s,CPPh₃)；¹³C{¹H}NMR(150.9MHz,CDCl_3、): δ=234.44 (br, C¹), 224.27 (t, J (P, C)=8.61Hz, C⁷),195.35(s,C¹⁰), 191.30 (dt, J (P, C)=30.23Hz, J (P, C)= 6.83Hz,C⁴), 173.47 (t, J (P, C)=6.61Hz, C¹¹),172.13(s,COOCH₃),163.57(s,C⁵),159.08(s, C⁶),152.58(s,C⁹),131.00(s,C⁸), 129.10 (d, J (P, C)=26.04Hz, C³), 127.03-134.36 (Ph and C⁸), 121.94 (d, J (P, C)=62.97Hz, C²), 120.51 (d, J (P, C)=87.61Hz, Ph), 121.10 (q, J (F, C) =321.51Hz, CF₃SO₃)64.10(s,C¹⁴),53.03(s,COOCH₃),37.00(s,C¹³),35.81(s,C¹⁵),25.34 (s,C¹²)；HRMS (ESI): m/z theoretical value [C₇₃H₆₂O₅P₃Ru]⁺1213.2848, measured value 1213.2857.

Embodiment 31

In above formula, [Ru]¹For RuCl (PPh₃)₂, [Ru]³For Ru (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of the compound V-1 in embodiment 30 of compound V-3 It is same:

Butine ketone used in embodiment 30 is changed into the dimethyl butyn of equimolar number.

Red solid compound V-3 is obtained, yield: 65% (mole that the yield of compound V-3 is compound V-3/ Mole × 100% of compound III-1).

The spectral data of metal bridge location fused ring compound V-3 obtained is as follows:

¹H NMR(600.1MHz,CDCl₃): δ=11.41 (d, J (P, H)=19.99,1H, C¹H),6.90-7.85(45H, ), Ph 6.22 (d, J (P, H)=3.50,1H, C³H),5.97(s,1H,C⁸H),3.82(s,6H,COOCH₃),3.73(s,3H, C¹²H),3.43(s,3H,C¹⁴H),2.96(s,2H,C¹⁷H),2.93(s,2H,C¹⁵H)；³¹P{¹H}NMR(242.9MHz,CDCl₃): δ=29.45 (s, RuPPh₃),9.47(s,CPPh₃)；¹³C{¹H}NMR(150.9MHz,CDCl₃): δ=228.93 (br, C¹), 207.05 (t, J (P, C)=7.40Hz, C⁷), 190.99 (dt, J (P, C)=30.72Hz, J (P, C)=7.08Hz, C⁴),, 175.10 (t, J (P, C)=7.05Hz, C¹⁰),172.16(s,COOCH₃),168.08(s,C¹³),161.48(s,C¹¹), 160.92(s,C⁵),158.64(s,C⁶),152.53(s,C⁹),130.39(s,C⁸), 127.10-134.54 (Ph and C⁸), 126.94 (d, J (P, C)=26.80Hz, C³), 123.28 (d, J (P, C)=62.95Hz, C²), 120.29 (d, J (P, C)= 87.97Hz, Ph), 121.14 (q, J (F, C)=321.21Hz, CF₃SO₃),64.08(s,C¹⁶),52.99(s,COOCH₃), 51.55(s,C¹²),51.39(s,C¹⁴),36.85(s,C¹⁷),35.81(s,C¹⁵) .HRMS (ESI): m/z theoretical value [C₇₅H₆₄O₈P₃Ru]⁺1287.2852, measured value 1287.2857.

Embodiment 32

In above formula, [Rh]¹For Rh (PPh₃)₂, [Rh]³For RhClPPh₃。

Under nitrogen atmosphere, toward compound III-11 (300mg, 0.23mmol) and sodium chloride made from embodiment 24 In methylene chloride (dosage of methylene chloride the is 15mL) solution of (133mg, 2.30mmol), phenyl propiolic acid methyl esters (117 is added μ L, 1.5mmol), green solution is obtained after reacting 1h at room temperature, filters, be concentrated into 2mL, 30mL ether or n-hexane is then added As precipitating reagent, the sediment of acquisition is filtered, washed, pillar layer separation (eluant, eluent are as follows: methylene chloride/acetone=8/1 body Product ratio), be spin-dried for obtaining compound V-22, yield: 73% (yield of compound V-22 be compound V-22 mole/compound Mole × 100% of III-11).

The spectral data of metal bridge location fused ring compound V-22 obtained is as follows:

¹H NMR(600.1MHz,CDCl₃): δ=11.46 (d, J (P, H)=19.87Hz, 1H, C¹H),6.96-7.79 (35H,Ph),6.85(s,C³H),5.92(s,1H,C⁸H),4.34(s,2H,C¹³H),4.11(s,2H,C¹⁴H),3.78(s,3H, C¹²H)；³¹P{¹H}NMR(242.9MHz,CDCl₃): δ=32.12 (d, J (Rh, P)=105.32Hz, RhPPh₃),7.21ppm (s,CPPh₃).

Embodiment 33

In above formula, [Ir]¹For Ir (PPh₃)₂, [Ir]³For IrClPPh₃。

In addition to following characteristics, the preparation method and the preparation method phase of compound V-22 in embodiment 32 of compound V-11 It is same:

Change compound III-11 used in embodiment 32 into made from the embodiment 23 of equimolar number compound III- 10, phenyl propiolic acid methyl esters is changed into the Methyl propiolate of equimolar number.

Obtain green solid compound V-11, yield: 73% (yield of compound V-11 be compound V-11 mole Amount/IrCl (PPh₃)₃Mole × 100%).

The spectral data of metal bridge location fused ring compound V-11 obtained is as follows:

¹H NMR(600.1MHz,CDCl₃): δ=11.40 (d, J (P, H)=19.51,1H, C¹H),7.57(s,1H, C⁹), H 6.93-7.82 (46H, Ph and C⁹H),6.15(s,1H,C³H),5.73(s,1H,C⁸H),4.12(s,2H,C¹³H),4.05 (s,2H,C¹⁴H),3.44(s,3H,C¹²H)；³¹P{¹H}NMR(242.9MHz,CDCl₃): δ=15.63 (s, CPPh₃),-2.31 (s,IrPPh₃).

Embodiment 34

In above formula, [Ru]¹For Ru (PPh₃)₂, [Ru]³For Ru ClPPh₃。

In addition to following characteristics, the preparation method of compound V-7 is identical as the preparation method of compound V-22 in embodiment 32:

Change compound III-11 used in embodiment 32 into made from the embodiment 18 of equimolar number compound III- 1, change phenyl propiolic acid methyl esters into equimolar number

Green solid compound V-7 is obtained, yield: 69% (mole that the yield of compound V-7 is compound V-7/ Mole × 100% of compound III-1).

The spectral data of metal bridge location fused ring compound V-7 obtained is as follows:

¹H NMR(600.1MHz,CDCl₃): δ=11.91 (d, J (P, H)=19.84,1H, C¹H),7.31(s,1H, C⁹), H 6.91-7.81 (55H, Ph and C⁹H),6.48(s,1H,C³H),5.53(s,1H,C⁸H),3.74(s,6H,COOCH₃), 2.65(s,4H,C¹²H and C¹³H)；³¹P{¹H}NMR(242.9MHz,CDCl₃): δ=28.35 (s, IrPPh₃),8.76(s, CPPh₃)；¹³C{¹H}NMR(150.9MHz,CDCl₃): δ=233.89 (br, C¹),212.65(br,C⁷),189.23(d,J(P, C)=32.08Hz, C⁴),171.11(s,COOCH₃),168.52(br,C¹⁰),161.36(s,C¹¹),160.12(s,C⁵), 155.21(s,C⁶),152.05(s,C⁹),129.32(s,C⁸), 126.46 (d, J (P, C)=24.64Hz, C³),127.14- 134.67 (Ph and C⁸), 121.74 (d, J (P, C)=63.44Hz, C²), 121.02 (q, J (F, C)=321.45Hz, CF₃SO₃), 119.35 (d, J (P, C)=87.31Hz, Ph), 64.140 (s, C¹³),52.16(s,COOCH₃),36.36(s,C¹²),35.94 (s,C¹⁴)；HRMS (ESI): m/z theoretical value [C₈₄H₆₉NO₄P₃Ru]⁺1350.3477, measured value 1350.3471.

Embodiment 35

Preparation method of the present embodiment to metal bridge location fused ring compound shown in formula VI.

In above formula, [Ru]⁴For RuCl₂PPh₃。

In addition to following characteristics, the preparation method and the preparation method phase of the compound I-1 in embodiment 1 of compound VI-1 It is same:

By HC ≡ CCH (OH) C ≡ CCH used in embodiment 1₂C(COOMe)₂CH₂C ≡ CH changes the preparation of equimolar number into HC ≡ CCH (OH) C ≡ CCH made from example 7₂C(COOMe)₂CH₂C≡CC≡CPh。

Obtain red solid compound VI-1, yield: 71% (yield of compound VI-1 be compound VI-1 mole Amount/RuCl₂(PPh₃)₃Mole × 100%).

¹H-NMR(600.1MHz,CDCl₃): δ=14.44 (ddd, J (PH)=16.61Hz, J (PH)=5.81Hz, J (HH) =2.99Hz, 1H, C¹), H 8.19 (dd, J (HH)=2.99Hz, J (PH)=2.04Hz, 1H, C³H),7.09-7.83(50H, Ph),3.74(s,3H,COOCH₃),3.51(s,3H,COOCH₃), 2.90 (d, J (HH)=19.79Hz, 1H, C¹²H),1.99(d, J (HH)=18.06Hz, 1H, C¹⁰), H 1.92 (d, J (HH)=19.79Hz, 1H, C¹²H), 1.61 (d, J (HH)=18.06Hz, 1H,C¹⁰H)；³¹P{¹H}NMR(242.9MHz,CDCl₃): δ=27.19 (d, J (PP)=4.66Hz, RuPPh₃),19.32(s, C⁸PPh₃),8.32(s,C²PPh₃).¹³C{¹H}NMR(150.5MHz,CDCl₃): δ=272.03 (br, C¹),209.49(dd,J (PC)=27.40Hz, J (PC)=5.64Hz, C⁷),205.96(s,C⁴),188.28(s,C⁵),170.52(s,COOCH₃), 170.36(s,COOCH₃),166.17(s,C⁸),160.80(s,C⁶), 150.76 (d, J (PC)=23.26Hz, C³),135.33 (d, J (PC)=64.64Hz, C⁹), 127.76-135.05 (m, Ph), 119.38 (d, J (PC)=87.70Hz, Ph), 105.64 (d, J (PC)=68.74Hz, C²),64.77(s,C¹¹),53.45(s,COOCH₃),53.35(s,COOCH₃),37.27(s, C¹²),36.84(s,C¹⁰) .HRMS (ESI): m/z theoretical value [C₇₆H₆₂Cl₂O₄P₃Ru]⁺,1303.2291；Measured value 1303.2285.

Embodiment 36

In above formula, [Rh]⁴For RhClPPh₃。

In addition to following characteristics, the preparation method and the preparation method phase of the compound I-1 in embodiment 1 of compound VI-13 It is same:

By HC ≡ CCH (OH) C ≡ CCH used in embodiment 1₂C(COOMe)₂CH₂C ≡ CH changes the preparation of equimolar number into HC ≡ CCH (OH) C ≡ CCH made from example 7₂C(COOMe)₂CH₂C ≡ CC ≡ CPh, by RuCl₂(PPh₃)₃Change equimolar number into RhCl(PPh₃)₃。

Obtain red solid compound VI-13, yield: 71% (yield of compound VI-13 is compound VI-13 Mole/RhCl (PPh₃)₃Mole × 100%).

¹H-NMR(600.1MHz,CD₂Cl₂): δ=14.32 (ddd, J (PH)=16.44Hz, J (PH)=5.78Hz, J (HH)=3.01Hz, 1H, C¹), H 7.84 (dd, J (HH)=3.18Hz, J (PH)=2.11Hz, 1H, C³H),7.04-7.76 (50H,Ph),3.63(s,3H,COOCH₃),3.44(s,3H,COOCH₃), 2.77 (d, J (HH)=19.86Hz, 1H, C¹²H), 1.82 (d, J (HH)=19.44Hz, 1H, C¹⁰), H 1.78 (d, J (HH)=19.93Hz, 1H, C¹²H), 1.56 (d, J (HH)= 18.67Hz,1H,C¹⁰H)；³¹P{¹H}NMR(242.9MHz,CD₂Cl₂): δ=25.63 (d, J (PP)=106.33Hz, RuPPh₃), 18.53(s,C⁸PPh₃),93.37(s,C²PPh₃).¹³C{¹H}NMR(150.5MHz,CD₂Cl₂): δ=273.12 (br, C¹), 210.18 (dd, J (PC)=27.44Hz, J (PC)=5.64Hz, C⁷),206.18(s,C⁴),188.84(s,C⁵),171.48(s, COOCH₃),170.62(s,COOCH₃),166.50(s,C⁸),161.43(s,C⁶), 151.93 (d, J (PC)=23.35Hz, C³), 136.47 (d, J (PC)=64.68Hz, C⁹), 128.35-136.43 (m, Ph), 118.99 (d, J (PC)=87.71Hz, Ph), 106.30 (d, J (PC)=68.73Hz, C²),66.10(s,C¹¹),54.70(s,COOCH₃),53.65(s,COOCH₃),37.68 (s,C¹²),37.55(s,C¹⁰) .HRMS (ESI): m/z theoretical value [C₇₆H₆₂ClO₄P₃Rh]⁺,1269.2599；Measured value 1269.2594.

Embodiment 37

In above formula, [Ir]⁴For IrClPPh₃。

In addition to following characteristics, the preparation method and the preparation method phase of the compound I-1 in embodiment 1 of compound VI-10 It is same:

By HC ≡ CCH (OH) C ≡ CCH used in embodiment 1₂C(COOMe)₂CH₂C ≡ CH changes the preparation of equimolar number into HC ≡ CCH (OH) C ≡ CCH made from example 12₂C(COOMe)₂CH₂C ≡ CC ≡ CTh (Th is thienyl), by RuCl₂(PPh₃)₃It changes At equimolar IrCl (PPh₃)₃。

Obtain red solid compound VI-10, yield: 73% (yield of compound VI-10 is compound VI-10 Mole/RhCl (PPh₃)₃Mole × 100%).

¹H-NMR(600.1MHz,CD₂Cl₂): δ=13.85 (ddd, J (PH)=16.89Hz, J (PH)=4.43Hz, J (HH)=2.42Hz, 1H, C¹), H 8.09 (dd, J (PH)=2.65Hz, J (HH)=2.65Hz, 1H, C³H),6.79-7.85 (49H,Ph),3.53(s,3H,COOCH₃),3.30(s,3H,COOCH₃), 2.31 (d, J (HH)=19.53Hz, 1H, C¹²H), 1.79 (d, J (HH)=18.06Hz, 1H, C¹⁰), H 1.61 (d, J (HH)=18.01Hz, 1H, C¹⁰H), 1.19 (d, J (HH)= 19.41Hz,1H,C¹²H)；³¹P{¹H}NMR(242.9MHz,CD₂Cl₂): δ=18.88 (s, C⁸PPh₃),9.51(s,C²PPh₃),- 12.42(s,IrPPh₃).¹³C{¹H}NMR(150.5MHz,CD₂Cl₂): δ=235.42 (br, C¹), 188.33 (d, J (PC)= 25.36Hz,C²), 182.57 (dd, J (PC)=4.20Hz, J (PC)=4.20Hz, C⁸),178.39(s,C⁵),170.42(s, COOCH₃),169.82(s,COOCH₃),163.10(s,C⁷),163.22(s,C⁶), 142.18 (d, J (PC)=22.49Hz, C³), 141.47 (d, J (PC)=70.68Hz, C⁹), 126.71-134.11 (m, Ph), 119.17 (d, J (PC)=88.27Hz, Ph), 98.24 (d, J (PC)=70.83Hz, C²),64.12(s,C¹¹),52.56(s,COOCH₃),52.23(s,COOCH₃),36.26 (s,C¹²),35.78(s,C¹⁰) .HRMS (ESI): m/z theoretical value [C₇₄H₆₀ClO₄P₃Ir]⁺,1365.2737；Measured value 1365.2734.

Embodiment 38

Preparation method of the present embodiment to the miscellaneous fused ring compound of osmium shown in formula I'.

Wherein, [Ru]¹For RuCl (PPh₃)₂。

Compound I-1 (0.1mmol) made from embodiment 1 is dissolved in 15mL chloroform, sodium hydroxide is then added (NaOH0.50mmol) and the mixed liquor of water (0.1mL) it, is filtered after the mixture of acquisition is stirred at room temperature 1 day, by filtrate It is concentrated into 2mL, 30mL n-hexane is added as precipitating reagent, the sediment of acquisition is filtered, washed and pillar layer separation (column color Spectrum filler is silica gel, eluant, eluent are as follows: methylene chloride/acetone=10/1 volume ratio) obtain red solid I'-1, yield: 78% (chemical combination The yield of object I'-1 is mole/compound I-1 mole × 100% of compound I'-1).

¹H NMR(300.1MHz,CD₂Cl₂): δ=13.15 (s, 1H, C⁷H),8.23(s,1H,C²H),7.45(s,1H, C³), H 6.98-7.94 (31H, Ph and C³H),3.72(s,6H,COOCH₃), 2.83 (t, J (H, H)=3.53, C¹⁰H),2.63(s, C⁸H)；³¹P{¹H}NMR(121.5MHz,CD₂Cl₂): δ=28.48 (s, RuPPh₃).

Embodiment 39

Wherein, [Ru]¹For RuCl (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of the compound I'-1 in embodiment 38 of compound I'-8 It is same:

Change compound I-1 used in embodiment 38 into made from the embodiment 3 of equimolar number compound I-8.

Obtain red solid compound I'-8, yield: 82% (yield of compound I'-8 be compound I'-8 mole Amount/compound I-8 mole × 100%).

¹H NMR(300.1MHz,CD₂Cl₂): δ=13.07 (s, 1H, C⁷H),8.12(s,1H,C²H),6.98-7.91 (35H,Ph),3.71(s,6H,COOCH₃), 2.82 (t, J (H, H)=3.53, C¹⁰H),2.62(s,C⁸H)；³¹P{¹H}NMR (121.5MHz,CD₂Cl₂): δ=28.03 (s, RuPPh₃).

Embodiment 40

Wherein, [Ir]¹For IrCl (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of the compound I'-1 in embodiment 38 of compound I'-7 It is same:

Change compound I-1 used in embodiment 38 into made from the embodiment 6 of equimolar number compound I-7.

Obtain red solid compound I'-7, yield: 81% (yield of compound I'-7 be compound I'-7 mole Amount/compound I-7 mole × 100%).

¹H-NMR(300.1MHz,CD₂Cl₂): δ=13.28 (s, 1H, C⁷H),8.01(s,C²H),7.55(s,1H,C³H), 6.59-7.73(m,30H,Ph),2.48(m,2H,C¹⁰H), 2.07 (tt, shows as quintet, J (HH)=7.27Hz, 2H, C⁹), H 1.73ppm (t, J (HH)=7.27Hz, 2H, C⁸H).³¹P{¹H}NMR(121.5MHz,CD₂Cl₂):-4.01ppm(s, IrPPh₃).

Embodiment 41

Wherein, [Rh]¹For Rh (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of compound I'-1 in embodiment 38 of compound I'-14 It is same:

Change compound I-1 used in embodiment 38 into made from the embodiment 8 of equimolar number compound I-14.

Obtain red solid compound I'-14, yield: 77% (yield of compound I'-14 is compound I'-14 Mole/compound I-14 mole × 100%).

¹H-NMR(300.1MHz,CD₂Cl₂): δ=13.12 (s, 1H, C⁷H),8.03(s,C²H),7.74(s,1H,C³H), 7.00-7.69(m,35H,Ph),2.61(m,2H,C¹⁰H), 2.07 (tt, shows as quintet, J (HH)=7.14Hz, 2H, C⁹), H 1.93ppm (t, J (HH)=7.14Hz, 2H, C⁸H).³¹P{¹H}NMR(121.5MHz,CD₂Cl₂): δ=35.02 (dd, J (RhP)=108.11Hz, J (PP)=5.56Hz, RhPPh₃).

Embodiment 42

Preparation method of the present embodiment to the miscellaneous fused ring compound of osmium shown in formula II'.

Wherein, [Ru]²For RuCO (PPh₃)₂。

In addition to following characteristics, the preparation method of compound II'-6 and the preparation method of the compound I'-1 in embodiment 38 It is identical:

Change compound I-1 used in embodiment 38 into made from the embodiment 15 of equimolar number compound II-6.

Obtain red solid compound II'-6, yield: 78% (yield of compound II'-6 is compound II'-6 Mole/compound II-6 mole × 100%).

¹H NMR(500.2MHz,CD₂Cl₂): δ=10.73 (s, 1H, C⁷), H 8.01 (d, 1H, J (HH)=7.2Hz, C³H), 7.92 (d, 1H, J (HH)=7.2Hz, C²H),6.03-7.81(35H,Ph),3.45(s,6H,COOCH₃),2.49(s,C¹⁰H), 2.23(s,C⁸H)；³¹P{¹H}NMR(202.5MHz,CD₂Cl₂): δ=35.94ppm (s, RuPPh₃).

Embodiment 43

Wherein, [Rh]²For RhCO (PPh₃)₂。

In addition to following characteristics, the preparation method of compound II'-2 and the preparation method of the compound I'-1 in embodiment 38 It is identical:

Change compound I-1 used in embodiment 38 into made from the embodiment 11 of equimolar number compound II-2.

Obtain red solid compound II'-2, yield: 71% (yield of compound II'-2 is compound II'-2 Mole/compound II-2 mole × 100%).

¹H-NMR(600.1MHz,CD₂Cl₂): δ=12.95 (s, 1H, C⁷H), 11.60 (d, J (HH)=7.8Hz, 1H, C¹), H 8.15 (d, 1H, J (HH)=7.3Hz, C³), H 7.93 (dd, 1H, J (HH)=7.8Hz, J (HH)=7.3Hz, C²H), 6.69-7.78(30H,Ph),2.18(m,2H,C¹⁰), H 1.44 (tt, J (HH)=7.28Hz, J (HH)=7.28Hz, 2H, C⁹H), 1.37ppm (t, J (HH)=7.28Hz, 2H, C⁸H)；³¹P{¹H}NMR(242.9MHz,CD₂Cl₂): δ=26.50ppm (dd, J (RhP)=109.11Hz, J (PP)=4.97Hz, RhPPh₃).

Embodiment 44

Wherein, [Ir]²For Ir CO (PPh₃)₂。

In addition to following characteristics, the preparation method of compound II'-9 and the preparation method of the compound I'-1 in embodiment 38 It is identical:

Change compound I-1 used in embodiment 38 into made from the embodiment 9 of equimolar number compound II-10.

Obtain red solid compound II'-9, yield: 75% (yield of compound II'-9 is compound II'-9 Mole/compound II-10 mole × 100%).

¹H-NMR(600.1MHz,CD₂Cl₂): δ=14.02 (s, 1H, C⁷H), 12.43 (d, J (HH)=8.11Hz, 1H, C¹), H 8.40 (d, 1H, J (HH)=7.5Hz, C³), H 8.12 (dd, 1H, J (HH)=8.11Hz, J (HH)=7.5Hz, C²H), 6.79-7.82(30H,Ph),2.23(m,2H,C¹⁰), H 1.41 (tt, J (HH)=7.32Hz, J (HH)=7.32Hz, 2H, C⁹H), 1.33ppm (t, J (HH)=7.32Hz, 2H, C⁸H)；³¹P{¹H}NMR(242.9MHz,CD₂Cl₂): δ=- 7.89ppm (s, IrPPh₃).

Embodiment 45

Preparation method of the present embodiment to the miscellaneous fused ring compound of osmium shown in formula III'.

Wherein, [Ru]¹For RuCl (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of compound I'-1 in embodiment 38 of compound III'-1 It is same:

Change compound I-1 used in embodiment 38 into made from the embodiment 19 of equimolar number compound III-20.

Obtain brown solid compound III'-1, yield: 81% (yield of compound III'-1 be compound III'-1 Mole/compound III-20 mole × 100%).

¹H NMR(300.1MHz,CD₂Cl₂): δ=12.13 (d, 1H, J (HH)=7.97Hz, C¹H),7.58(d,1H,J (HH)=7.39Hz, C³), H 7.46 (dd, 1H, J (HH)=7.97Hz, J (HH)=7.39Hz, C²H),6.56-7.81(37H, Ph、C³H and C²H),3.58(s,6H,COOCH₃),3.52(s,1H,C⁸H),3.22(s,C¹¹H),2.36(s,C⁹H)；³¹P{¹H} NMR(121.5MHz,CD₂Cl₂): δ=22.06ppm (s, RuPPh₃).

Embodiment 46

Wherein, [Ru]¹For RuCl (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of compound I'-1 in embodiment 38 of compound III'-8 It is same:

Change compound I-1 used in embodiment 38 into made from the embodiment 21 of equimolar number compound III-8.

Obtain red solid compound III'-8, yield: 85% (yield of compound III'-8 be compound III'-8 Mole/compound III-8 mole × 100%).

¹H NMR(600.1MHz,CD₂Cl₂): δ=12.01 (d, J (HH)=8.56Hz, 1H, C¹H),6.85(1H,C³H, determined by ¹H-¹³C HSQC and ¹H-¹³C HMBC),6.63(1H,C²H,determined by ¹H-¹³C HSQC and ¹H-¹³C HMBC),6.54-7.82(32H,Ph、C³H and C²H),3.75(s,6H,COOCH₃),2.65(s,C⁸H), 2.54ppm(s,C¹⁰H)；³¹P{¹H}NMR(242.9MHz,CD₂Cl₂): δ=23.62ppm (s, RuPPh₃).

Embodiment 47

Wherein, [Ir]¹For Ir (PPh₃)₂。

In addition to following characteristics, the preparation method of compound I'-1 in the preparation method and embodiment 38 of compound III'-10 It is identical:

Change compound I-1 used in embodiment 38 into made from the embodiment 23 of equimolar number compound III-10.

Obtain red solid compound III'-10, yield: 81% (yield of compound III'-10 be compound The mole of III'-10/compound III-10 mole × 100%).

¹H-NMR(500.2MHz,CD₂Cl₂): δ=13.95 (d, 1H, J (HH)=8.52Hz, C¹H),8.43(d,J(HH) =7.39Hz, 1H, C³), H 8.23 (dd, 1H, J (HH)=8.52Hz, J (HH)=7.39Hz, C²H),6.76-8.02(m,30H, Ph),4.50(s,2H,C⁹H),3.63(s,2H,C¹⁰H),3.17ppm(s,2H,C⁸H)；³¹P{¹H}NMR(202.5MHz, CD₂Cl₂): δ=- 15.34ppm (s, IrPPh₃).

Embodiment 48

Wherein, [Rh]¹For Rh (PPh₃)₂。

In addition to following characteristics, the preparation method of compound I'-1 in the preparation method and embodiment 38 of compound III'-14 It is identical:

Change compound I-1 used in embodiment 38 into made from the embodiment 25 of equimolar number compound III-14.

Obtain red solid compound III'-14, yield: 81% (yield of compound III'-14 be compound The mole of III'-14/compound III-10 mole × 100%).

¹H-NMR(400.1MHz,CDCl₃): δ=13.65 (d, J (HH)=8.76Hz, 1H, C¹H),8.54(d,1H,J (HH)=7.26Hz, C³), H 8.23 (dd, 1H, J (HH)=8.76Hz, J (HH)=7.26Hz, C²H),7.95–6.78ppm(m, 30H,Ph),2.69(m,2H,C¹⁰), H 1.75 (tt, J (HH)=7.61Hz, 2H, C⁹H), 1.36 (t, J (HH)=7.61Hz, 2H, C⁸H).³¹P-NMR(162.0MHz,CDCl₃): δ=- 9.3ppm (s, J (RhP)=110.21Hz, RhPPh₃).

Embodiment 49

Preparation method of the present embodiment to the miscellaneous fused ring compound of osmium shown in formula IV'.

Wherein, [Rh]¹For Rh (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of compound I'-1 in embodiment 38 of compound IV'-9 It is same:

Change compound I-1 used in embodiment 38 into made from the embodiment 28 of equimolar number compound IV-8.

Obtain green solid compound IV'-9, yield: 86% (yield of compound IV'-9 is compound IV'-9 Mole/compound IV-8 mole × 100%).

¹H NMR(300.1MHz,CD₂Cl₂): δ=12.59 (d, 1H, J (H, H)=8.62Hz, C¹H),6.88-7.76 (35H, Ph), 8.37 (d, 1H, J (H, H)=8.62Hz, C²H),7.65(s,1H,C³H),5.54(s,1H,C⁸H),3.54(q,J (H, H)=7.19Hz, OCH₂CH₃),2.43(m,2H,C¹²H), 2.02 (tt, shows as quintet, J (HH)=7.26Hz, 2H, C¹¹), H 1.79ppm (t, J (HH)=7.26Hz, 2H, C¹⁰), H 1.22 (t, J (H, H)=7.19Hz, OCH₂CH₃)；³¹P{¹H}NMR (121.5MHz,CD₂Cl₂): δ=24.59ppm (d, J (RhP)=102.72Hz, RhPPh₃).

Embodiment 50

Wherein, [Ru]¹For RuCl (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of compound I'-1 in embodiment 38 of compound IV'-5 It is same:

Change compound I-1 used in embodiment 38 into made from the embodiment 27 of equimolar number compound IV-5.

Obtain green solid compound IV'-5, yield: 84% (yield of compound IV'-5 is compound IV'-5 Mole/compound IV-5 mole × 100%).

¹H NMR(300.1MHz,CD₂Cl₂): δ=11.95 (d, 1H, J (HH)=8.57Hz, C¹H),6.83-7.72 (35H, Ph), 6.11 (d, 1H, J (HH)=7.12Hz, C³), H 5.67 (d, 1H, J (HH)=7.12Hz, C²H),2.74(s, COCH₃),3.52(s,C¹⁰H),3.43(s,C¹¹H)；³¹P{¹H}NMR(121.5MHz,CD₂Cl₂): δ=20.36ppm (s, RuPPh₃).

Embodiment 51

Wherein, [Ir]¹For Ir (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of compound I'-1 in embodiment 38 of compound IV'-12 It is same:

Change compound I-1 used in embodiment 38 into made from the embodiment 29 of equimolar number compound IV-12.

Obtain green solid compound IV'-12, yield: 87% (yield of compound IV'-12 be compound IV'-12 Mole/compound IV-12 mole × 100%).

¹H NMR(300.1MHz,CD₂Cl₂): δ=11.89 (d, 1H, J (HH)=8.53Hz, C¹H),6.75-7.66 (35H, Ph), 6.45 (d, 1H, J (HH)=8.53Hz, C²H),3.53(s,6H,COOCH₃), 3.36 (q, J (H, H)=7.12Hz, OCH₂CH₃),2.48(s,C¹⁰H),2.26(s,C¹²), H 1.29 (t, J (H, H)=7.12Hz, OCH₂CH₃)；³¹P{¹H}NMR (121.5MHz,CD₂Cl₂): δ=- 8.32ppm (s, IrPPh₃).

¹H NMR(300.1MHz,CD₂Cl₂): δ=11.89 (d, 1H, J (HH)=8.53Hz, C¹H),6.75-7.66 (35H, Ph), 6.65 (d, 1H, J (HH)=8.53Hz, C²H),6.53(s,1H,C³H), 3.63 (q, J (H, H)=7.10Hz, OCH₂CH₃),2.41(m,2H,C¹²), H 2.21 (tt shows as quintet, J (HH)=6.95Hz, 2H, C¹¹H),1.83ppm(t, J (HH)=6.95Hz, 2H, C¹⁰), H 1.30 (t, J (H, H)=7.10Hz, OCH₂CH₃)；³¹P{¹H}NMR(121.5MHz, CD₂Cl₂): δ=- 8.32ppm (s, IrPPh₃).

Embodiment 52

Preparation method of the present embodiment to the miscellaneous fused ring compound of osmium shown in formula V'.

Wherein, [Ru]³For Ru (PPh₃)₂。

In addition to following characteristics, the preparation method and the preparation method phase of the compound I'-1 in embodiment 38 of compound V'-1 It is same:

Change compound I-1 used in embodiment 38 into made from the embodiment 30 of equimolar number compound V-1.

Obtain green solid compound V'-1, yield: 80% (yield of compound V'-1 be compound V'-1 mole Amount/compound V-1 mole × 100%).

¹H NMR(600.1MHz,CDCl₃): δ=11.23 (d, J (HH)=8.62Hz, 1H, C¹H),7.78(d,1H,J (HH)=7.23Hz, C⁹), H 6.90-7.81 (31H, Ph and C⁹), H 6.39 (d, 1H, J (HH)=7.12, C³H),6.11(dd, 1H, J (HH)=8.62Hz, J (HH)=7.12, C²), H 5.85 (d, 1H, J (HH)=7.23Hz, C⁸H),3.76(s,6H, COOCH₃),2.94(s,4H,C¹³H and C¹⁵H),1.31(s,3H,C¹²H)；³¹P{¹H}NMR(242.9MHz,CDCl₃): δ= 32.84(s,RuPPh₃).

Embodiment 53

Wherein, [Ir]³For IrClPPh₃。

In addition to following characteristics, the preparation method of compound V'-11 and the preparation method of the compound I'-1 in embodiment 38 It is identical:

Change compound I-1 used in embodiment 38 into made from the embodiment 33 of equimolar number compound V-11.

Obtain green solid compound V'-11, yield: 88% (yield of compound V'-11 is compound V'-11 Mole/compound V-11 mole × 100%).

¹H NMR(600.1MHz,CDCl₃): δ=11.58 (d, 1H, J (HH)=8.69Hz, C¹H),7.63(d,1H,J (HH)=7.31Hz, C⁹), H 6.95-7.89 (31H, Ph and C⁹), H 6.45 (d, 1H, J (HH)=7.15Hz, C³H),6.23(dd, 1H, J (HH)=8.69Hz, J (HH)=7.15Hz, C²), H 5.53 (d, 1H, J (HH)=7.31Hz, C⁸H),4.12(s,2H, C¹³H),4.05(s,2H,C¹⁴H),3.54(s,3H,C¹²H)；³¹P{¹H}NMR(242.9MHz,CDCl₃): δ=- 4.56ppm (s, IrPPh₃).

Embodiment 54

Wherein, [Rh]³For RhClPPh₃。

In addition to following characteristics, the preparation method and the preparation method phase of compound I'-1 in embodiment 38 of compound V'-22 It is same:

Change compound I-1 used in embodiment 38 into made from the embodiment 32 of equimolar number compound V-22.

Obtain green solid compound V'-22, yield: 88% (yield of compound V'-22 is compound V'-22 Mole/compound V-22 mole × 100%).

¹H NMR(600.1MHz,CDCl₃): δ=12.57 (d, 1H, J (HH)=8.92Hz, C¹H),6.89-7.58(20H, Ph),6.81(s,C³), H 6.54 (d, 1H, J (HH)=8.92Hz, C²H),5.90(s,1H,C⁸H),4.31(s,2H,C¹³H), 4.07(s,2H,C¹⁴H),3.72(s,3H,C¹²H)；³¹P{¹H}NMR(242.9MHz,CDCl₃): δ=35.93ppm (d, J (Rh, P) =103.32Hz, RhPPh₃).

Embodiment 55

Preparation method of the present embodiment to the miscellaneous fused ring compound of osmium shown in formula VI'.

Wherein, [Ru]⁴For RuCl₂PPh₃。

In addition to following characteristics, the preparation method and the preparation method phase of compound I'-1 in embodiment 38 of compound VI'-1 It is same:

Change compound I-1 used in embodiment 38 into made from the embodiment 35 of equimolar number compound VI-1.

Obtain red solid compound VI'-1, yield: 88% (yield of compound VI'-1 is compound VI'-1 Mole/compound VI-1 mole × 100%).

¹H-NMR(600.1MHz,CDCl₃): δ=14.44 (d, 1H, J (HH)=8.56Hz, C¹H), 8.19 (d, J (HH)= 7.23Hz,1H,C³), H 8.02 (dd, J (HH)=8.56Hz, J (HH)=7.23Hz, C²H),6.89-7.93(35H,Ph),3.79 (s,3H,COOCH₃),3.46(s,3H,COOCH₃), 2.87 (d, J (HH)=20.03Hz, 1H, C¹²H), 1.99 (d, J (HH)= 19.63Hz,1H,C¹⁰), H 1.92 (d, J (HH)=20.03Hz, 1H, C¹²), H 1.61 (d, J (HH)=19.63Hz, 1H, C¹⁰H) ；³¹P{¹H}NMR(242.9MHz,CDCl₃): δ=32.58 (s, RuPPh₃),21.05ppm(s,C⁸PPh₃).

Embodiment 56

Wherein, [Ir]⁴For IrClPPh₃。

In addition to following characteristics, the preparation method and the preparation method phase of compound I'-1 in embodiment 38 of compound VI'-10 It is same:

Change compound I-1 used in embodiment 38 into made from the embodiment 37 of equimolar number compound VI-10.

Obtain red solid compound VI'-10, yield: 82% (yield of compound VI'-10 be compound VI'-10 Mole/compound VI-10 mole × 100%).

¹H-NMR(600.1MHz,CD₂Cl₂): δ=13.85 (d, J (HH)=8.96Hz, 1H, C¹H),9.35(d,J(HH) =7.19Hz, 1H, C³), H 8.52 (dd, 1H, J (HH)=8.96Hz, J (HH)=7.19Hz, C²H),6.83-7.91(33H, Ph),3.65(s,3H,COOCH₃),3.42(s,3H,COOCH₃), 2.36 (d, J (HH)=19.82Hz, 1H, C¹²H),1.83(d, J (HH)=18.26Hz, 1H, C¹⁰), H 1.74 (d, J (HH)=18.26Hz, 1H, C¹⁰H), 1.36 (d, J (HH)=19.82Hz, 1H,C¹²H)；³¹P{¹H}NMR(242.9MHz,CD₂Cl₂): δ=21.36 (s, C⁸PPh₃),-15.69ppm(s,IrPPh₃).

Embodiment 57

Wherein, [Rh]⁴For RhClPPh₃。

In addition to following characteristics, the preparation method and the preparation method phase of compound I'-1 in embodiment 38 of compound VI'-13 It is same:

Change compound I-1 used in embodiment 38 into made from the embodiment 36 of equimolar number compound VI-13.

Obtain red solid compound VI'-13, yield: 83% (yield of compound VI'-13 be compound VI'-13 Mole/compound VI-13 mole × 100%).

¹H-NMR(600.1MHz,CD₂Cl₂): δ=13.21 (d, J (HH)=8.32Hz, 1H, C¹H),8.31(d,J(HH) =7.60Hz, 1H, C³), H 8.01 (dd, J (HH)=8.32Hz, J (HH)=7.60Hz, 1H, C²H),6.78-7.96(35H, Ph),3.68(s,3H,COOCH₃),3.48(s,3H,COOCH₃), 2.79 (d, J (HH)=19.89Hz, 1H, C¹²H),1.84(d, J (HH)=19.46Hz, 1H, C¹⁰), H 1.79 (d, J (HH)=19.89Hz, 1H, C¹²H), 1.57 (d, J (HH)=19.46Hz, 1H,C¹⁰H)；³¹P{¹H}NMR(242.9MHz,CD₂Cl₂): δ=27.61 (d, J (PP)=106.33Hz, RuPPh₃),13.51(s, C⁸PPh₃).

Test case 1

This test case is used to uv-visible absorption spectra and the application of the miscellaneous fused ring compound of metal shown in formula I.

It is carried out using representative compound I-1 of the SHIMADZU UV2550 spectrometer to the Formulas I obtained in above-described embodiment Uv-visible absorption spectra test.The condition of test are as follows: compound I-1 is diluted to 1.0 × 10 using methylene chloride^-5mol/ L is tested at room temperature.

As shown in FIG. 1, FIG. 1 is the ultraviolet-visibles for the metal bridge location fused ring compound I-1 that above-described embodiment 1 is prepared Abosrption spectrogram.

As seen from Figure 1, compound I-1 has wide absorption (280nm~650nm) in ultraviolet-visible light region, There is absorption maximum at wavelength 575nm, therefore can be used as the photosensitizer of solar battery.

Test case 2

This test case is used to uv-visible absorption spectra and the application of the miscellaneous fused ring compound of metal shown in formula II.

Representative compound II-1 using SHIMADZU UV2550 spectrometer to the Formula II obtained in above-described embodiment example Uv-visible absorption spectra test is carried out with II-11.The condition of test are as follows: use methylene chloride by compound II-1 and II-11 It is diluted to 1.0 × 10 respectively^-5Mol/L is tested at room temperature.

Fig. 2 is the UV-visible absorption spectrum of metal bridge location fused ring compound II-1.

Fig. 3 is the UV-visible absorption spectrum of metal bridge location fused ring compound II-11.

Compound II-1 and II-11 has wider absorption in ultraviolet-visible light region it can be seen from Fig. 2 and Fig. 3 (being 280nm~600nm), compound II-1 have absorption maximum at wavelength 530nm, and compound II-11 is in wavelength 490nm Place has absorption maximum, therefore can be used as the photosensitizer of solar battery.

Test case 3

This test case is used to circulation-volt-ampere curve and the application of the miscellaneous fused ring compound of metal shown in formula II.

(1) circulation-volt-ampere curve

Using glass-carbon electrode as working electrode, platinum electrode is to electrode, and silver/silver chlorate is reference electrode, nitrogen atmosphere, room temperature Under, the representative compound II-2 of Formula II recycle in the dichloromethane solution of the tetrabutyl ammonium hexafluorophosphate of 0.1M- Volt-ampere electrochemistry can be carried out test.

As shown in figure 4, having surely reversible oxidation peak, explanation at+1.33V when compound II-2 anode forward scan Its oxidation state is more stable；When the scanning of cathode negative sense, there is surely reversible reduction peak at -0.79V, illustrate that its reduction-state is more steady It is fixed；It is aoxidized and reduction half wave potential V_1/2Respectively+1.29V and -0.75V.And it is used for the photosensitizer that photodissociation aquatic products hydrogen produces oxygen, For its ideal redox half wave potential between+1.3V and -0.9V, the redox half wave potential of compound II-2 is located at should In section, therefore compound II-2 may be used as the photosensitizer that photodissociation aquatic products hydrogen produces oxygen.

(2) application as catalyst in lithium-air battery

In addition, there are two pairs of reversible redox peaks based on compound II-2, and potential difference is more than+2.0V, again Its application in lithium-air battery is probed into.Using DMSO as electrolyte, compound II-2 is tested to lithium-air The influence of charging, discharging electric batteries current potential.

As shown in figure 5, compound II-2 can effectively reduce the charging potential of lithium-air battery.Therefore, compound II-2 can To be applied in lithium-air battery as lithium storage materials.

Test case 4

This test case is used to uv-visible absorption spectra and the application of the miscellaneous fused ring compound of metal shown in formula IV.

(1) uv-visible absorption spectra of compound IV-1

Using SHIMADZU UV2550 spectrometer to the representative compound IV-1 of the formula IV obtained in above-described embodiment into The test of row uv-visible absorption spectra.The condition of test are as follows: compound IV-1 is diluted to 1.0 × 10 using methylene chloride^- ⁵Mol/L is tested at room temperature.

As shown in fig. 6, Fig. 6 is the UV-visible absorption spectrum of metal bridge location fused ring compound IV-1.

As seen from Figure 6, compound IV-1 has wide absorption (280nm~750nm) in ultraviolet-visible light region, There is absorption maximum at wavelength 620nm.

(2) purposes measurement of the compound IV-1 in photodynamic therapy for cancer

Photodynamic therapy principle: molecule is under light illumination by ground state S₀Transit to singlet excited state S₁(step 1), S₁Spoke Ground state S is returned to after projecting fluorescence₀(step 2) generates triplet state T by intersystem crossing₁(step 3), T₁With ground state oxygen (three lines State) effect generation singlet oxygen (step 4),¹O₂And then it is sensitized killing tumour cell.

(1)S₀(Sensor)+hν→S₁；

(2)S₁→S₀+hν(Fluo)；

(3)S₁→T₁；

(4)T₁+³O₂→S₀+¹O₂；

(5)¹O₂+ matrix → oxidation.

Active oxygen detection is carried out using fluorescence probe DCFH-DA.DCFH-DA itself can be generated without fluorescence by basic hydrolysis DCFH.Active oxygen can aoxidize non-blooming DCFH and generate the DCF for having fluorescence.The fluorescence of DCF is detected it is known that in system The level of active oxygen.

There is the absorption peak of the last one near 630nm using compound IV-1, with laser light source used in photodynamic therapy Wavelength 630nm matching.According to document (Li-Sen Lin, Zhong-Xiao Cong, Juan Li, Kai-Mei Ke, Shan- Shan Guo,Huang-Hao Yang,Guo-Nan Chen,Graphitic-phase C₃N₄nanosheets as efficient photosensitizers and pH-responsive drug nanocarriers for cancer Imaging and therapy, J.Mater.Chem.B, 2014,2,1031) the external activity oxygen test experiments condition of report, Configure isometric DCFH fluorescence probe and sample solution, 630nm laser irradiation after five minutes, with 488nm laser detection its Fluorescence intensity at 525nm, it is as shown in Figure 7 to measure result.

As seen from Figure 7, with the raising of sample concentration, the fluorescence intensity of probe DCFH with enhancing, illustrate in system because Photosensitizer and the active oxygen amount that generates increases.This illustrates that compound IV-1 can be used for photodynamic therapy.

Test case 5

This test case is used to uv-visible absorption spectra and the application of the miscellaneous fused ring compound of metal shown in formula V.

It is carried out using representative compound V-3 of the SHIMADZU UV2550 spectrometer to the Formula V obtained in above-described embodiment Uv-visible absorption spectra test.The condition of test are as follows: compound V-3 is diluted to 1.0 × 10 using methylene chloride^-5mol/ L is tested at room temperature.

As shown in figure 8, Fig. 8 is the UV-visible absorption spectrum of metal bridge location fused ring compound V-3.

As seen from Figure 8, compound V-3 has wide absorption (280nm~750nm) in ultraviolet-visible light region, There is absorption maximum at wavelength 640nm, therefore can be used as the photosensitizer of solar battery and controlled for tumor photodynamic It treats.

Test case 6

This test case is used to uv-visible absorption spectra and the application of the miscellaneous fused ring compound of metal shown in formula VI.

Using SHIMADZU UV2550 spectrometer to the representative compound VI-1 of the Formula IV obtained in above-described embodiment into The test of row uv-visible absorption spectra.The condition of test are as follows: compound VI-1 is diluted to 1.0 × 10 using methylene chloride^- ⁵Mol/L is tested at room temperature.

As shown in figure 9, Fig. 9 is the UV-visible absorption spectrum of metal bridge location fused ring compound VI-1.

As seen from Figure 9, compound VI-1 has wide absorption (280nm~700nm) in ultraviolet-visible light region, There is absorption maximum at wavelength 570nm, therefore can be used as the photosensitizer of solar battery.

Test case 7

This test case is used to uv-visible absorption spectra and the application of the miscellaneous fused ring compound of metal shown in formula III.

Using SHIMADZU UV2550 spectrometer to the representative compound III-9 of the formula III obtained in above-described embodiment Carry out uv-visible absorption spectra test.The condition of test are as follows: compound III-9 is diluted to 1.0 using methylene chloride × 10^-5Mol/L is tested at room temperature.

As shown in Figure 10, Figure 10 is the UV-visible absorption spectrum of metal bridge location fused ring compound III-9.

As seen from Figure 10, compound III-9 ultraviolet-visible light region have wide absorption (300nm~ 750nm), there is absorption maximum at wavelength 625nm, therefore can be used as the photosensitizer of solar battery and be used for tumour light Photodynamic therapy.

Test case 8

This test case is used to uv-visible absorption spectra and the application of the miscellaneous fused ring compound of metal shown in formula I'.

Using SHIMADZU UV2550 spectrometer to the Formulas I obtained in above-described embodiment ' representative compound I'-6 into The test of row uv-visible absorption spectra.The condition of test are as follows: compound I'-6 is diluted to 1.0 × 10 using methylene chloride^- ⁵Mol/L is tested at room temperature.

As shown in figure 11, Figure 11 is the UV-visible absorption spectrum of metal bridge location fused ring compound I'-6.

As seen from Figure 11, compound I'-6 has wide absorption (300nm~600nm) in ultraviolet-visible light region, There is absorption maximum at wavelength 447nm, therefore can be used as the photosensitizer of solar battery.

Test case 9

This test case is used to uv-visible absorption spectra and the application of the miscellaneous fused ring compound of metal shown in formula II'.

Using SHIMADZU UV2550 spectrometer to the Formula II obtained in above-described embodiment ' representative compound II'-9 Carry out uv-visible absorption spectra test.The condition of test are as follows: compound II'-9 is diluted to 1.0 using methylene chloride × 10^-5Mol/L is tested at room temperature.

As shown in figure 12, Figure 12 is the UV-visible absorption spectrum of metal bridge location fused ring compound II'-9.

As seen from Figure 12, compound II'-9 ultraviolet-visible light region have wide absorption (300nm~ 600nm), there is absorption maximum at wavelength 490nm, therefore can be used as the photosensitizer of solar battery.

Test case 10

This test case is used to the uv-visible absorption spectra of the miscellaneous fused ring compound of metal shown in formula III' and answers With.

Using SHIMADZU UV2550 spectrometer to the formula III obtained in above-described embodiment ' representative compound III'-4 carries out uv-visible absorption spectra test.The condition of test are as follows: be diluted to compound III'-4 using methylene chloride 1.0×10^-5Mol/L is tested at room temperature.

As shown in figure 13, Figure 13 is the UV-visible absorption spectrum of metal bridge location fused ring compound III'-4.

As seen from Figure 13, compound III'-4 ultraviolet-visible light region have wide absorption (300nm~ 800nm), there is absorption maximum at wavelength 665nm, therefore can be used as the photosensitizer of solar battery and be used for tumour light Photodynamic therapy.

Test case 11

This test case is used to uv-visible absorption spectra and the application of the miscellaneous fused ring compound of metal shown in formula IV'.

Using SHIMADZU UV2550 spectrometer to the formula IV obtained in above-described embodiment ' representative compound IV'-5 Carry out uv-visible absorption spectra test.The condition of test are as follows: compound IV'-5 is diluted to 1.0 using methylene chloride × 10^-5Mol/L is tested at room temperature.

As shown in figure 14, Figure 13 is the UV-visible absorption spectrum of metal bridge location fused ring compound IV'-5.

As seen from Figure 14, compound IV'-5 ultraviolet-visible light region have wide absorption (300nm~ 900nm), there is absorption maximum at wavelength 690nm, therefore can be used as the photosensitizer of solar battery and be used for tumour light Photodynamic therapy.

Test case 12

This test case is used to uv-visible absorption spectra and the application of the miscellaneous fused ring compound of metal shown in formula V'.

Using SHIMADZU UV2550 spectrometer to the Formula V obtained in above-described embodiment ' representative compound V'-1 into The test of row uv-visible absorption spectra.The condition of test are as follows: compound V'-1 is diluted to 1.0 × 10 using methylene chloride^- ⁵Mol/L is tested at room temperature.

As shown in figure 15, Figure 15 is the UV-visible absorption spectrum of metal bridge location fused ring compound V'-1.

As seen from Figure 15, compound V'-1 has wide absorption (300nm~750nm) in ultraviolet-visible light region, There is absorption maximum at wavelength 650nm, therefore can be used as the photosensitizer of solar battery and be used for tumor photodynamic Treatment.

Test case 13

This test case is used to uv-visible absorption spectra and the application of the miscellaneous fused ring compound of metal shown in formula VI'.

Using SHIMADZU UV2550 spectrometer to the Formula IV obtained in above-described embodiment ' representative compound VI'- 11 carry out uv-visible absorption spectra test.The condition of test are as follows: compound VI'-11 is diluted to 1.0 using methylene chloride ×10^-5Mol/L is tested at room temperature.

As shown in figure 16, Figure 16 is the UV-visible absorption spectrum of metal bridge location fused ring compound VI'-11.

As seen from Figure 16, compound VI'-11 ultraviolet-visible light region have wide absorption (300nm~ 750nm), there is absorption maximum at wavelength 620nm, therefore can be used as the photosensitizer of solar battery and be used for tumour light Photodynamic therapy.

The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims

1. a kind of metal bridge location fused ring compound, which is characterized in that the compound has structure as shown below:

Wherein,

In Formula IV and VI', [M]⁴For RuA₂L, RhAL or IrAL；

Wherein, in VI or VI', A is any one in-H, halogen ,-SCN and-CN；

L is in Phosphine ligands, CO ligand, pyridine, nitrogen heterocycle carbine ligand, nitrile ligand and isocyanide class bielectron ligand It is at least one；The pyridine is the ligand containing pyridine or bipyridyl structural unit；The nitrile ligand is to contain nitrile The ligand of based structures unit；The isocyanide class bielectron ligand is the ligand containing isonitrile based structures unit；

R₁ ⁺Cationic substituent in any one in position to indicate digital 1-5 in Formula IV, and R₁ ⁺It is 3-30 The quaternary ammonium cation of carbon atom quaternary phosphine cation or 3-24 carbon atom；

R₂For at least one of position for indicating digital 1-5,8 in Formula IV, and and R₁ ⁺The different substitution in position Base；

R₃For positioned at Formula IV ' on indicate digital 1-5,8 at least one of position on substituent group；

R₂And R₃Respectively independently selected from-H, halogen ,-SCN ,-CN, alkyl, alkoxy, alkylthio group, the acyl of 1-20 carbon atom Base, ester group, amido, amide groups, carboxyl, the amide groups of 2-20 substituted carbon atom, the naphthenic base of 3-20 carbon atom replace Or unsubstituted aryl, the alkenyl of substituted or unsubstituted 2-20 carbon atom, substituted or unsubstituted 2-20 carbon atom Alkynyl, aryloxy group, the arylthio of 1-20 carbon atom, and any one in water-soluble substituent group can be improved；

Wherein, it can be polyethylene glycol residue, hyaluronic acid residue, polyacrylic acid and sugar that the energy, which improves water-soluble substituent group, Any one in analog derivative residue；The carbohydrate derivative residue refers to that any one hydroxyl of carbohydrate derivative removes hydrogen Remaining part after atom, the carbohydrate derivative are glucose, sucrose, maltose, galactolipin, lactose, fructose and sialic acid Derivative in any one；

Alternatively, be located at Formula IV or Formula IV ' on indicate the position 1,2-, the position 2,3- and 4 of digital 1-5, at the position 5- at least One upper substituted or unsubstituted cyclic substituents；

In Formula IV, Z^-For Cl^-、Br^-、I^-、BF₄ ^-、CF₃SO₃ ^-、CH₃COO^-、(CF₃SO₂)₂N^-、NO₃ ^-、ClO₄ ^-、PF₆ ^-And BPh₄ ^-In Any one.

2. compound according to claim 1, wherein

L be trimethyl-phosphine, triethyl phosphine, tripropyl phosphine, tri isopropyl phosphine, tri-tert-butylphosphine, tricyclohexyl phosphine, triphenylphosphine, Picoline, ethylpyridine, 1,4- bipyridyl, 1,2- bis- (4- pyridyl group) ethylene, vinylpyridine, ethynyl pyridine, pyridine Boric acid, aminopyridine, cyanopyridine, mercaptopyridine, dimethylamino pyridine, phenylpyridine, 1,2- bis- (4- pyridyl group) ethane, miaow Azoles type N-heterocyclic carbine, imidazoline type N-heterocyclic carbine, thiazole type N-heterocyclic carbine, triazole type N-heterocyclic carbine, acetonitrile, third At least one of nitrile, cyanophenyl, cyclohexyl isocyanide, tert-butyl isocyanide and phenyl isocyanide；

R₁ ⁺Cationic substituent in any one in position to indicate digital 2-5 in Formula IV, and R₁ ⁺It is 5-23 The quaternary ammonium cation of carbon atom quaternary phosphine cation or 5-20 carbon atom；

R₂On at least one of position to indicate number 1,2,3,4,5 and 8 in Formula IV, and and R₁ ⁺Position is different Substituent group；

R₃For positioned at Formula IV ' on indicate number 1,2,3,4,5 and 8 at least one of position on substituent group；

R₂And R₃Respectively independently selected from-H, halogen ,-SCN ,-CN, alkyl, alkoxy, alkylthio group, the acyl of 1-17 carbon atom Base, ester group, amido, amide groups, carboxyl, the amide groups of 2-17 substituted carbon atom, the naphthenic base of 3-17 carbon atom replace Or unsubstituted aryl, the alkenyl of substituted or unsubstituted 2-17 carbon atom, substituted or unsubstituted 2-17 carbon atom Alkynyl, aryloxy group, the arylthio of 2-17 carbon atom, and at least one of water-soluble substituent group can be improved；Wherein, institute It can be that polyethylene glycol residue, hyaluronic acid residue, polyacrylic acid and carbohydrate derivative are residual that water-soluble substituent group can be improved by, which stating, Any one in base；The carbohydrate derivative residue refers to remaining after any one hydroxyl of carbohydrate derivative removes hydrogen atom Part, the carbohydrate derivative is in the derivative of glucose, sucrose, maltose, galactolipin, lactose, fructose and sialic acid Any one；

Alternatively, be located at Formula IV or Formula IV ' on indicate the position 2,3- and/or 4 of digital 1-5, it is substituted or unsubstituted on the position 5- Cyclic substituents.

3. compound according to claim 2, wherein R₁ ⁺It is any in position to indicate number 2 and 5 in Formula IV Cationic substituent on one, and R₁ ⁺For the quaternary ammonium sun of 6-18 carbon atom quaternary phosphine cation or 6-18 carbon atom from Son；

R₂On at least one of position to indicate number 1,4,5 and 8 in Formula IV, and and R₁ ⁺Position is different to be taken Dai Ji；

R₃For positioned at Formula IV ' on indicate number 1,4,5 and 8 at least one of position on substituent group；

R₂And R₃The amide groups of alkyl, 2-8 substituted carbon atom respectively independently selected from 1-8 carbon atom, 3-8 carbon The naphthenic base of atom, the alkenyl of substituted or unsubstituted 2-8 carbon atom, the alkynyl of substituted or unsubstituted 2-8 carbon atom, Aryloxy group, the arylthio of 2-8 carbon atom；

4. compound according to claim 3, wherein

R₁ ⁺For trimethyl-phosphine, triethyl phosphine, tripropyl phosphine, tri isopropyl phosphine, tri-tert-butylphosphine, tricyclohexyl phosphine, triphenylphosphine, Appointing in Trimethylamine, triethylamine, one ethylamine of dimethyl, tripropyl ammonium, triisopropyl ammonium and tri-tert ammonium cation It anticipates one kind；

R₂And R₃Respectively independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, N-pentyl, isopentyl, neopentyl, sec-amyl, tertiary pentyl, n-hexyl, isohesyl, new hexyl, Sec-Hexyl, tertiary hexyl, n-heptyl, Different heptyl, new heptyl, Zhong Gengji, tertiary heptyl, n-octyl, iso-octyl, new octyl, secondary octyl, t-octyl, dodecyl, just Cetyl, n-octadecane base, n-eicosane base, Methoxyl group, ethoxy It is base, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, new Amoxy, secondary amoxy, tertiary amoxy, positive hexyloxy, dissident's oxygroup, new hexyloxy, secondary hexyloxy, tertiary hexyloxy, positive oxygen in heptan Base, different oxygroup in heptan, new oxygroup in heptan, Zhong Geng oxygroup, tertiary oxygroup in heptan, n-octyloxy, different octyloxy, new octyloxy, secondary octyloxy, uncle Octyloxy, n-dodecane oxygroup, hexadecane oxygroup, n-octadecane oxygroup, n-eicosane oxygroup, methyl mercapto, ethylmercapto group, positive third Sulfenyl, isopropyisulfanyl, positive butylthio, isobutylthio, secondary butylthio, tertiary butylthio, positive penta sulfenyl, isopentylthio, new penta sulfenyl, Secondary penta sulfenyl, tertiary penta sulfenyl, just own sulfenyl, isohexylthio, new own sulfenyl, secondary own sulfenyl, tertiary own sulfenyl, positive sulfenyl in heptan, different heptan Sulfenyl, new sulfenyl in heptan, Zhong Geng sulfenyl, tertiary sulfenyl in heptan, just pungent sulfenyl, different pungent sulfenyl, new pungent sulfenyl, Zhong Xin sulfenyl, tertiary pungent sulfenyl, N-dodecane sulfenyl, hexadecane sulfenyl, n-octadecane sulfenyl, n-eicosane sulfenyl,

Methylamino, ethylamino-, Propylamino, Butylamine base, amylamine base, hexylamine base, heptyl amice base, octylame base, dimethylamino, diethylin, dipropyl amido, dibutyl amino, positive 12 Amido, hexadecylamine base, octadecyl amine base, positive 20 amido, Cyclopropyl, cyclobutyl, cyclopenta, ring Hexyl, suberyl, cyclooctyl, cyclo-dodecyl, ring cetyl, ring octadecyl, ring eicosyl, phenyl, naphthalene, anthracene Base, phenanthryl, pyrenyl, thienyl, furyl, pyridyl group, pyrrole radicals, Phenoxy group, naphthoxy, anthracene oxygroup, luxuriant and rich with fragrance oxygroup, Pyrene oxygroup, thiophene oxy, furans oxygroup, pyridine oxygroup, pyrroles's oxygroup, p- toloxyl, m- toloxyl, adjacent toluene oxygen Base, p- nitro-phenoxy, p- methoxyphenoxy, thiophenyl, naphthalene sulfenyl, anthracene sulfenyl, luxuriant and rich with fragrance sulfenyl, pyrene sulfenyl, thiophene thio, Furansulfenyl, pyridine thio, pyrroles's sulfenyl, p- Tolylsulfanvl, m- Tolylsulfanvl, adjacent Tolylsulfanvl, p- nitrophenylsulfenyl, At least one in p- Methoxv-phenylsulfanvl, polyethylene glycol residue, hyaluronic acid residue, polyacrylic acid and carbohydrate derivative residue Kind；The carbohydrate derivative residue refers to that any one hydroxyl of carbohydrate derivative removes remaining part after hydrogen atom, described Carbohydrate derivative is any one in the derivative of glucose, sucrose, maltose, galactolipin, lactose, fructose and sialic acid.

5. compound according to claim 1, wherein the cyclic substituents are the ternary being all made of carbon atom Ring, four-membered ring, five-membered ring, hexatomic ring, heptatomic ring or octatomic ring substituent group, or by containing at least one in aerobic, sulphur, nitrogen and silicon Three-membered ring, four-membered ring, five-membered ring, hexatomic ring, heptatomic ring or the octatomic ring substituent group of a hetero atom composition.

6. compound according to claim 5, wherein the substituent group of the substituted cyclic substituents is that 1-20 carbon is former The alkyl of son, the ester group of 1-20 carbon atom, the acyl group of 1-20 carbon atom, the carboxyl of 1-20 carbon atom, substitution do not take The aryl in generation, the naphthenic base of 3-8 carbon atom, itrile group, nitro andAt least one of；Wherein, R₃₀It is 1-20 Any one in the alkyl of carbon atom and substituted or unsubstituted phenyl.

7. compound according to claim 6, wherein R₃₀For the alkyl and substituted or unsubstituted benzene of 1-17 carbon atom Any one in base.

8. compound according to claim 7, wherein R₃₀For the alkyl and substituted or unsubstituted benzene of 1-14 carbon atom Any one in base.

9. compound according to claim 8, wherein

The substituted or unsubstituted cyclic substituents are In any one.

10. compound according to claim 1, wherein

A is any one in H, F, Cl, Br and SCN；

L is at least one of CO ligand, triphenylphosphine ligand, trimethyl-phosphine ligand, triethyl phosphine ligand；

In Formula IV, Z^-For Cl^-、Br^-、BF₄ ^-、CF₃SO₃ ^-、PF₆ ^-And BPh₄ ^-In any one；

R₁ ⁺The cationic substituent on position to indicate number 2 or 5 in Formula IV, and R₁ ⁺For triphenylphosphine cation, three Methylphosphine cation, triethyl phosphine cation, Trimethylamine cation and triethylamine cation in any one；

R₂And R₃Respectively independently selected from-H ,-F ,-Cl ,-Br ,-SCN ,-CN ,-OPh ,-SPh, In any one；

The position 2,3- or 4 in Formula IV and VI' has cyclic substituents at the position 5-, and the cyclic substituents are In any one.

11. compound according to claim 1, wherein the metal bridge location fused ring compound is in following compound Any one:

In the above compound, [Ru]⁴For RuA₂PPh₃, [Rh]⁴For RhAPPh₃, [Ir]⁴For IrAPPh₃；

Wherein, A H, Cl or SCN.

12. the preparation method of compound described in any one of claim 1-11, which is characterized in that this method comprises:

Pass through cycloaddition reaction preparation formula with ruthenium complex, rhodium complex and complex of iridium respectively using Formula IX compound represented VI compound represented；

Wherein, G is-O- ,-S- ,-CR₁₈R₁₉-、-SiR₂₀R₂₁And-NR₂₂In any one；

Wherein, R₉、R₁₀And R₁₃The range and R for the substituent group that can be selected₂Or R₃It is identical；

M and n is respectively the integer of 1-6, and m+n < 8；

The ruthenium complex is RuCl₂(PPh₃)₃、RuCl₂(PMe₃)₃、RuCl₂(PEt₃)₃And RuCl₂(PCy₃)₃In at least one Kind；

The rhodium complex is RhCl (PPh₃)₃、RhHCl₂(PPh₃)₃、RhCl(PMe₃)₃、RhCl(PEt₃)₃With RhCl (PCy₃)₃ At least one of；

The complex of iridium is IrHCl₂(PPh₃)₃、IrCl(PPh₃)₃、IrCl(PMe₃)₃、IrCl(PEt₃)₃With IrCl (PCy₃)₃ At least one of；

The alkali 2 is the hydroxide of alkali metal.

13. according to the method for claim 12, wherein

The alkali 2 is NaOH and/or KOH；

The concentration of the aqueous solution of the alkali 2 is 0.01-10 mol/L.

14. according to the method for claim 13, wherein the concentration of the aqueous solution of the alkali 2 is 0.5-5 mol/L.

15. according to the method for claim 12, wherein

The condition of the cycloaddition reaction includes that reaction temperature is -100-200 DEG C；Reaction time is -2 days 1 minute；

All reactions carry out in the presence of an organic；The organic solvent is methylene chloride, dichloroethanes, chlorine Imitative, methanol, ethyl alcohol, acetone, butanone, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, toluene, benzene, dioxane, At least one of ether and acetonitrile.

16. according to the method for claim 15, wherein

The condition of the cycloaddition reaction includes that reaction temperature is 0-60 DEG C；Reaction time is -1 day 0.5 hour.

17. compound described in any one of claim 1-11 is in solar battery, photodynamic therapy, photocatalytic water, lithium-sky Application in gas field of batteries.

18. application according to claim 17, wherein

Formula IV compound represented is suitable for area of solar cell；

Formula IV ' compound represented is suitable for photodynamic therapy field.

19. application according to claim 17, wherein

In Formula IV compound represented, R₂To indicate the substituent group in number 1,2,3 or 8, and R₂For aryl；Indicate digital 1-5's The position the 2,3- or position 4,5- is substituted or unsubstituted cyclic substituents；

In Formula IV ' compound represented, R₃To indicate digital 1-5, the substituent group on 8, R₃For the alkoxy of 1-20 carbon atom； Indicate substituted or unsubstituted cyclic substituents on the position 2,3- or the position 4,5- of digital 1-5.

20. application according to claim 19, wherein

In Formula IV compound represented, R₂To indicate the substituent group in number 8, and R₂For phenyl；Indicate the position 4,5- of digital 1-5 It sets and locates substituted or unsubstituted cyclic substituents；The cyclic substituents are the five-membered ring being all made of carbon atom or hexa-atomic Ring substituents, or the five-membered ring or hexatomic ring that are made of together any one and the carbon atom in oxygen, nitrogen and silicon atom replace Base；When substituent group on the substituted cyclic substituents is the ester group of 1-20 carbon atom, Formula IV compound represented is applicable in In area of solar cell；

In Formula IV ' compound represented, R₃Substituted or unsubstituted cyclic substituents at the position 4,5- to indicate digital 1-5； The cyclic substituents are the five-membered ring or hexa-atomic ring substituents being all made of carbon atom, or by oxygen, nitrogen and silicon atom Any one and carbon atom five-membered ring or hexa-atomic ring substituents for forming together；Substitution on the substituted cyclic substituents When base is the ester group of 1-20 carbon atom, Formula IV ' compound represented is suitable for photodynamic therapy for cancer.

21. application according to claim 20, wherein

When substituent group on the substituted cyclic substituents is the ester group of 1-20 carbon atom, Formula IV compound represented is used as The photosensitizer of solar battery.