CN108383862A - A kind of indeno [2,1-b] indyl rare earth metal complex and preparation method thereof - Google Patents
A kind of indeno [2,1-b] indyl rare earth metal complex and preparation method thereof Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
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- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
Abstract
The present invention relates to a kind of indeno [2,1 b] indyl rare earth metal complexs and preparation method thereof, shown in the rare earth metal complex such as chemical formula [I]:Wherein, Ln is the transition metal element of Group IIIB in the periodic table of elements;Z1And Z2It is same or different to each other;DnFor the neutral ligand being coordinated with rare earth metal, and n is the integer more than or equal to 0;L is by the removing of chemical formula [II] compound and R6Hydrogen on connected carbon atom is formed by substituent group:Wherein, R1To R10It is identical or different, and R2To R5In and R7To R10In have at least two adjacent groups that can form substituted or unsubstituted aliphatic ring or aromatic ring by linking together.
Description
Technical field
Technical field is related to a kind of new catalyst for olefines polymerizing and preparation method thereof, and in particular to a kind of indenes
And [2,1-b] indyl rare earth metal complex and preparation method thereof, the complex is especially suitable for high-cis olefin rubber
Preparation.
Background technology
Olefin rubber is the key that olefinic rubber production technology with catalyst system, the caltalyst owner used at present
There are nickel (Ni) system, titanium (Ti) system, cobalt (Co) system, rare earth neodymium (Nd) system and lithium (Li) system etc..Wherein, rare earth catalyst is this
Most characteristic and high comprehensive performance kind in a little catalyst system and catalyzings, with olefinic rubber cis-structure content height, the line of its production
Shape structural integrity is high, molecular weight is high and narrowly distributing.The use of more rare earth catalyst is at present ternary Nd-based catalyst, is
Multicenter class ziegler-natta catalyst systems.
Compared to polycentric class ziegler-nata rare-earth catalysis system, homogeneous single centre rare-earth metal catalyst activity
Higher, dosage are few and are easily dispersed, are easier to make for the regulation and control of polymerization activity, polymer molecular weight and regularity.Currently, with
In conjugated diene stereospecfic polymerization have specific structure single centre rare-earth metal catalyst (including cyclopentadienyl rare-earth metal catalyst and
Non-metallocene rare earth metallic catalyst) research obtained preferable development.
Taube et al. has found that luxuriant neodymium allyl complex constitutes the catalyst of high activity with lewis acid appropriate
(J.Organomet.Chem., 2001,621,327.) Boisson and Monteil et al. reports two luxuriant neodymiums and two of silicon bridging
Fluorenes Nd complex catalyst, realize butadiene and-alkene combined polymerization (Macromol.Chem.Phys., 2003,204,
1747;Macromol.Chem.Phys.,2004,205,737;Angew.Chem.,2005,117,2649;
Angew.Chem.Int.Ed.,2005,44,2593.).Kaita using bis- (pentamethylcyclopentadiene) bases stabilization shirt and gadolinium
Complex compound has been catalyzed to high activity butadiene or isoprene in the presence of modified methylaluminoxane (MMAO) or borate
It is cis- -1,4 polymerization (Macromolecules 1999,32,9078-9079;Macromolecules 2001,34,1539-
1541;Macromolecules 2003,36,7923-7926;Macromolecules 2004,37,5860-5862;
Macromolecules 2006,39,1359-1363).In addition, the amine compound for the gadolinium that double indenyls are stablized, in borate
Also excellent polymerization (Dalton Trans., 2008,2531-2533) is shown under activation.The non-cyclopentadienyl of Hou Zhaomin research and development
PNP rare earth compounds (Angew.Chem.Int.Ed.2007,46,1909-1913) and Cui Dongmei research and development NCN it is dilute
Earth metal complex (J.Am.Chem.Soc.2008,130,4984-4991), Butadiene or isoamyl in the presence of borate
Diene can carry out the polymerization of high-cis -1,4.
The ligand that searching is suitable for rare earth metal is a main research direction of Organolanthanide Chemistry.Indeno
[2,1-b] indoles is the cyclopentadiene derivant of a kind of electron rich, is widely used in the 4th group 4 transition metal organic compound
Synthesis.Traditional indeno [2,1-b] indole derivatives synthetic method (US6232260, US6908972, US6559251,
US5554775, US5539124, US5637660, US5902866), catalyst is made using a large amount of concentrated sulfuric acids, and synthetic yield is not
Height is only adapted to laboratory and prepares on a small scale, and is not suitable for extensive ligand and prepares.Patent (CN106905223A) and document
It is new that (Chinese Chemical Letters 2017,28 (3), 569-574.) discloses indeno [2,1-b] indolyl derivatives
Synthetic method, the ammonium salt of hydrazine is replaced using aryl, can be succeeded in single organic solvent without any external acid catalyst
Indeno [2,1-b] indoles is synthesized, yield is close to 100%;It can be carried out on indoles N atoms in the presence of a nickel catalyst abundant
Substitution reaction prepares indeno [2,1-b] indole derivatives of multiple types N- alkyl and aryl substitution, and yield is very high.Indeno
The 4th group 4 transition metal organic compound (such as KR2015015791, KR that [2,1-b] indolyl derivatives are stablized
2015015789、WO 2015016423、WO 2015016422、WO 2002092647、WO9924446、CN1249756A、
CN1805980A, WO2009/032048A1, WO2009/032051A1, WO2015/016423A1), there is C2Symmetry or Cs
Symmetrical structure, catalyst system and catalyzing can synthesize the polyolefin products of different performance for ethylene or propylene polymerization.Patent (CN
105985368, CN 105985383, PCT CN2016073644) use indeno [2,1-b] indolyl derivatives and the 4th race's transition
The organic compound of metal has quasi- C2Symmetrical structure, and show preferable catalytic performance to ethylene or propylene, can be with
Regulate and control the structure of homopolymerization block polymer.But in Organolanthanide Chemistry field, application of such compound as ligand
It is less.Therefore, indeno [2,1-b] indoles is as the synthesis of the rare earth metal complex of ligand and its application of catalysis in olefine polymerization
Wait to study.
Invention content
To solve the above-mentioned problems, it is an object of the invention to develop a kind of indeno [2,1-b] indyl rare earth metal to match
Object and preparation method thereof is closed, which can be as the catalyst for preparing high-cis olefinic rubber.
For this purpose, the present invention provides a kind of indeno [2,1-b] indyl rare earth metal complex, by following below formula [I] table
Show:
Wherein, Ln is the transition metal element of Group IIIB;
Z1And Z2It is identical or different, it is respectively selected from protium, halogen, alkyl-R, silylation-SiR each independently3, alkane
Oxygroup-OR, sulfydryl-SR, carboxyl-OCOR, amido-NR2With phosphino--PR2In one kind, wherein R be selected from by C1-C20's
Saturated alkyl, the unsaturated alkenyl of C2-C20, the naphthenic base of C3-C20, the aryl or aralkyl of C6-C30 and its derivative, C1-
C30's contains group III A in the periodic table of elements to the heteroatomic alkyl of V Group IIA element, aryl or aralkyl and its derivative
One kind in the formed group of object;
DnFor the neutral ligand being coordinated with Ln, and n is the integer more than or equal to 0;
L is that the hydrogen on the carbon atom being connected with R6 by the removing of chemical formula [II] compound is formed by substituent group:
Wherein, R1To R10It is identical or different, be respectively selected from each independently by hydrogen, halogen, C1-C20 saturated alkyl,
The unsaturated alkenyl of C2-C20, the naphthenic base of C3-C20, the aryl of C6-C30 and its derivative, C7-C30 aralkyl and its derivative
Object, C1-C30 containing group III A in the periodic table of elements to the heteroatomic alkyl of V Group IIA element, aryl or aralkyl and
One kind in the formed group of its derivative, and R2To R5In and R7To R10In have at least two adjacent groups that can pass through
It links together and forms substituted or unsubstituted aliphatic ring or aromatic ring.
Indeno [2,1-b] indyl rare earth metal complex of the present invention, wherein the Ln is preferably selected from scandium, yttrium
And one kind in lanthanide rare metallic element.
Indeno [2,1-b] indyl rare earth metal complex of the present invention, wherein Z1And Z2Separately preferably
Selected from trimethylsilyl methyl, two (trimethyl silyl) methyl, three (trimethyl silyl) methyl, o- (N, N-
Dimethylamino) benzyl, N, one kind in N- bis- (trimethyl silyl) amido, but not limited to this.
Indeno [2,1-b] indyl rare earth metal complex of the present invention, wherein the saturated alkyl of the C1-C20
One be preferably selected from methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, amyl, hexyl, heptyl, octyl
Kind, but not limited to this;
The unsaturated alkenyl of the C2-C20 is preferably selected from vinyl, acrylic, allyl, cyclobutenyl, pentenyl
One kind, but not limited to this;
The naphthenic base of the C3-C20 is preferably selected from one kind in cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, but unlimited
In this;
The aryl and its derivative of the C6-C30 are preferably selected from one kind in phenyl, xenyl, naphthalene, phenanthryl, fluorenyl,
But not limited to this;
The aralkyl and its derivative of the C7-C30 is preferably selected from benzyl, p-methylphenyl, o-methyl-phenyl, methyl
Phenyl, adjacent 3,5-dimethylphenyl, 3,5-dimethylphenyl, mesitylene base, adjacent diisopropyl phenyl, to one in tert-butyl-phenyl
Kind, but not limited to this;
The C1-C30's contains group III A in the periodic table of elements to the heteroatomic alkyl of V Group IIA, aryl, aralkyl
Base and its derivative be preferably selected from chloromethyl, bromomethyl, iodomethyl, chloroethyl, bromoethyl, iodine ethyl, trimethyl silyl,
Triethylsilyl, tripropylsilyl base, tributylsilyl, triisopropylsilyl, trimethyl silyl
Methyl, dimethylamino, diethylin, diisopropyl amido, methoxyl group, ethyoxyl, cyano, nitro, trifluoromethyl, to fluorobenzene
Base, rubigan, p-bromophenyl, p-trifluoromethyl phenyl, p-methoxyphenyl, to cyano-phenyl, p-nitrophenyl, to diformazan
One kind in aminocarbonyl phenyl, but not limited to this.
Indeno [2,1-b] indyl rare earth metal complex of the present invention, wherein DnBe preferably selected from tetrahydrofuran,
One kind in ether, thiophene, pyridine, pyrroles, imidazoles, carbazole, oxazole, triphenylphosphine, but not limited to this, further preferably four
Hydrogen furans, ether, thiophene or pyridine, pyridine therein are more preferably 2,6- lutidines, 4,4- bipyridyls.
The present invention also provides a kind of preparation methods of indeno [2,1-b] indyl rare earth metal complex, are above-mentioned
The preparation method of complex, includes the following steps:
By chemical formula [II] compound and with trisubstituted rare earth compound LnZ3After heating, pass through acid-base reaction
Indeno [2,1-b] indyl rare earth metal complex of the Dan Mao is made;
Above-mentioned acid-base reaction carries out in reaction dissolvent;
LnZ3In, Ln is the transition metal element of Group IIIB;
Z is selected from protium, halogen, alkyl-R, silylation-SiR3, alkoxy-OR, sulfydryl-SR, carboxyl-OCOR,
Amido-NR2With phosphino--PR2In one kind, wherein R be selected from by the saturated alkyl of C1-C20, C2-C20 unsaturated alkenyl,
The naphthenic base of C3-C20, the aryl or aralkyl of C6-C30 and its derivative, C1-C30 contain Section III A in the periodic table of elements
Race is to one kind in the heteroatomic alkyl of V Group IIA element, aryl or aralkyl and its formed group of derivative;
Chemical formula [II] compound is as follows:
Wherein, R1To R10It is identical or different, be respectively selected from each independently by hydrogen, halogen, C1-C20 saturated alkyl,
The unsaturated alkenyl of C2-C20, the naphthenic base of C3-C20, the aryl of C6-C30 and its derivative, C7-C30 aralkyl and its derivative
The heteroatomic alkyl of transition metal element element, aryl or the aralkyl containing Group IIIB in the periodic table of elements of object, C1-C30
One kind in base and its formed group of derivative, and R2To R5In and R7To R10In at least two adjacent group energy
It is enough to form substituted or unsubstituted aliphatic ring or aromatic ring by linking together.
The preparation method of indeno [2,1-b] indyl rare earth metal complex of the present invention, wherein the soda acid is anti-
The reaction temperature answered is preferably 0 DEG C~120 DEG C, further preferably 40 DEG C~80 DEG C.
The preparation method of indeno [2,1-b] indyl rare earth metal complex of the present invention, wherein the Z is preferred
Selected from trimethylsilyl methyl, two (trimethyl silyl) methyl, three (trimethyl silyl) methyl, o- (N, N-
Dimethylamino) benzyl, N, one kind in N- bis- (trimethyl silyl) amido.
The preparation method of indeno [2,1-b] indyl rare earth metal complex of the present invention, wherein the reaction is molten
Agent is preferably selected from least one of toluene, hexane, ether, tetrahydrofuran.
The present invention also provides a kind of preparation methods of indeno [2,1-b] indyl rare earth metal complex, are above-mentioned
The preparation method of complex, includes the following steps:
S1 carries out lithiation by alkyl lithium reagents and chemical formula [II] compound and obtains lithiated product;
S2 is by lithiated product and LnX3Carry out indeno [2,1-b] the indyl rare earth metal pair that Dan Mao is made in salt elimination reaction
Halide;
The double halide of indeno [2,1-b] the indyl rare earth metal of Dan Mao with nucleophilic displacement of fluorine reagent eliminate anti-by S3
It answers, indeno [2,1-b] the indyl rare earth metal complex is made;
Above-mentioned S1, S2 and S3 are carried out in organic solvent;
Wherein, chemical formula [II] compound is as follows:
Wherein, R1To R10It is identical or different, be respectively selected from each independently by hydrogen, halogen, C1-C20 saturated alkyl,
The unsaturated alkenyl of C2-C20, the naphthenic base of C3-C20, the aryl of C6-C30 and its derivative, C7-C30 aralkyl and its derivative
The heteroatomic alkyl of transition metal element element, aryl or the aralkyl containing Group IIIB in the periodic table of elements of object, C1-C30
One kind in base and its formed group of derivative, and R2To R5In and R7To R10In at least two adjacent group energy
It is enough to form substituted or unsubstituted aliphatic ring or aromatic ring by linking together;
LnX3Middle Ln is the transition metal element of Group IIIB;X is halogen.
The preparation method of indeno [2,1-b] indyl rare earth metal complex of the present invention, wherein X be preferably chlorine,
Bromine or iodine.
Indeno [2,1-b] indyl rare earth metal complex of the present invention, wherein the reaction temperature of the lithiation
Preferably -80 DEG C~25 DEG C, further preferably -40 DEG C~0 DEG C of degree;The reaction temperature of the salt elimination reaction is preferably -80
DEG C~25 DEG C, further preferably -40 DEG C~0 DEG C;The reaction temperature of the elimination reaction is preferably -80 DEG C~25 DEG C, into one
Preferably -40 DEG C~0 DEG C of step.
Indeno [2,1-b] indyl rare earth metal complex of the present invention, wherein the alkyl lithium reagents preferably select
From at least one of lithium methide, n-BuLi, tert-butyl lithium, lithium diisopropyl amido.
Indeno [2,1-b] indyl rare earth metal complex of the present invention, wherein the nucleophilic displacement of fluorine reagent is preferred
Selected from trimethylsilyl methyl lithium, two (trimethyl silyl) lithium methides, three (trimethyl silyl) lithium methides,
O- (N, N- dimethylamino) benzyl lithium, N, at least one of N- bis- (trimethyl silyl) amido lithium.
Indeno [2,1-b] indyl rare earth metal complex of the present invention, wherein the organic solvent is preferably selected from
At least one of toluene, hexane, ether, tetrahydrofuran.
The specific structural diagrams of chemical formula [II] compound are as follows, but not limited to this:
The concrete structure diagram for the complex that chemical formula [I] indicates is as follows, but not limited to this.Wherein, Ln=Sc, Y and
Lanthanide rare metallic element, R=CH2SiMe3Or CH2C6H4(NMe2)-o, work as R=CH2SiMe3When, DnIn, D=THF, n are big
In or equal to 1 integer (depending on rare earth central metallic ions radius):
The preparation method of indeno [2,1-b] indyl rare earth metal complex provided by the invention, can be by preparing as follows
Route A and route B indicate:
Wherein, X can be halogen, preferably chlorine, bromine, iodine;
Preparation route A is by indeno [2,1-b] indole derivatives and between trisubstituted rare earth compound
Acid-base reaction, be made Dan Mao indeno [2,1-b] indyl rare earth metal complex.Reaction temperature is chosen as 0 DEG C~120
DEG C, it preferably 40 DEG C~80 DEG C, is carried out preferably according to substituent group and the different of rare earth metal type;The optional toluene of reaction dissolvent, oneself
Alkane, ether, tetrahydrofuran, preferably toluene.
In preparation route B, first by alkyl lithium reagents to indeno [2,1-b] indole derivatives carry out lithiumation, then with
Rare earth metal trihalid carries out the double halide of indeno [2,1-b] indyl rare earth metal that Dan Mao is made in salt elimination reaction, most
Elimination reaction is carried out with the nucleophilic displacement of fluorine reagent of 2 molecules afterwards, indeno [2,1-b] indyl rare earth metal complex is made.Reaction
- 78 DEG C of temperature~room temperature, preferably -30 DEG C~room temperature;The optional toluene of reaction dissolvent, hexane, ether, tetrahydrofuran, preferably
Tetrahydrofuran.
Indeno [2,1-b] indyl rare earth metal complex of the present invention can be used for producing olefin polymer, have aobvious
The activity of work, and olefin polymer has preferable three-dimensional regularity.
Specific implementation mode
It elaborates below to the embodiment of the present invention:The present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
The synthesized reference patent (CN 106905223A) of indeno [2,1-b] indole derivatives, Rare earth metal precursors compound
(such as rare earth metal tribenzyl based compound Ln (CH2C6H4NMe2-o)3) synthesized reference document (Chem.Eur.J.2008,14,
2167-2179.) carry out.
The synthesis of indeno [2,1-b] indyl rare earth metal complex unless otherwise specified under the conditions of anhydrous and oxygen-free into
Row is realized by inert atmosphere glove box or Schlenk technologies.It tests solvent for use and passes through anhydrous and oxygen-free processing.
In addition, the nuclear magnetic resonance of rare earth metal complex1H-NMR spectrum is surveyed by Bruker Ascend600MHz
Examination, part complex can not be carried out due to paramagnetic properties1H-NMR is characterized.Cis- -1,4 selectivity of polymer passes through13C-NMR
Spectrogram determines, and closes mode for gated decoupling without NOE;The molecular weight and molecular weight distribution of polymer pass through PL-GPC50 gel infiltrations
Chromatograph is tested.
Embodiment 1
Weigh 1.15g N- methyl indeno [2,1-b] indoles (Fw=respectively in the Schlenk bottles of 2 100mL
219.28,5.25mmol) and 2.46g Y (CH2C6H4NMe2-o)3(Fw=491.50,5mmol) is dissolved in respectively in 30mL toluene
Solution is made.At ambient temperature, the toluene solution (light brown) of N- phenyl indeno [2,1-b] indoles is slowly added drop-wise to Y
(CH2C6H4NMe2-o)3Toluene solution (faint yellow) in, then continue at room temperature stirring 1 hour.Then, reaction bulb is set
70 DEG C are heated in oil bath, and the reaction was continued 12 hours, reaction solution gradually becomes buff from faint yellow.Reaction terminates
Afterwards, solvent is extracted under vacuum, obtains pale tan oil, 20mL n-hexanes are added, solid is precipitated, filtered and with a small amount of n-hexane
Brownish-yellow powder solid 2.05g (Fw=575.58), yield 71.3% are obtained after washing 2 times.
Nuclear magnetic data:1H-NMR(600MHz,C6D6):1.74(s,4H),2.21(s,12H,N-Me),3.10(s,3H,N-
), Me 5.02 (s, 1H), 6.62 (m, 2H), 6.69 (t, 2H, J=6Hz), 6.86 (m, 2H), 6.92 (m, 1H), 7.06 (m, 1H),
7.28 (m, 5H), 7.42 (d, 1H, J=6Hz), 7.73 (d, 1H, J=6Hz), 7.89 (d, 1H, J=6Hz)
Embodiment 2
Weighed in Schlenk bottles of 200mL 4.38g N- methyl indeno [2,1-b] indoles (Fw=219.28,
20mmol), 100mL anhydrous ether wiring solution-formings are added.- 25 DEG C are cooled to, the hexane that n-BuLi is then slowly added dropwise is molten
Liquid (2.4M, 9.2mL, 22mmol), solution gradually becomes glassy yellow, and is generated with yellow insoluble matter.It is allowed after being added dropwise
Naturally be warmed to room temperature, and continue to be stirred to react 2 hours at room temperature, solvent is extracted under vacuum after having reacted, be used in combination it is anhydrous just oneself
Alkane washs 2 times, obtains light yellow solid powder 4.46g (Fw=225.21), is lithium salts intermediate product, yield 99%.
Embodiment 3
The anhydrous YCl of 0.39g are weighed in Schlenk bottles of 100mL320mL tetrahydrochysene furans are added in (Fw=195.26,2mmol)
It mutters (through water removal), heating stirring 10 hours at 60 DEG C.Subsequent vacuum extracts THF, obtains white powdery solids YCl3
(THF)3.5, it is directly used in next step.
Claim N- methyl indeno [2,1-b] indyl lithium salts 0.450g (Fw=225.21,2mmol) to be dissolved in anhydrous THF to be made
Solution.Then at -25 DEG C, it is slowly dropped to YCl3(THF)3.5In the THF suspensions of (2mmol), allowed after being added dropwise
It is warmed to room temperature naturally, and continues to be stirred to react 12 hours at room temperature.THF is extracted after the completion of reaction under vacuum, residue is used
Dry toluene extracts, and collects filtrate after suction filtration, and extract toluene under vacuum, and it is N- methyl indeno [2,1- to obtain yellow solid
B] indyl dichloride yttrium, it is directly used in next step.
Above-mentioned N- methyl indeno [2,1-b] indyl dichloride yttrium intermediate product is dissolved in dry toluene wiring solution-forming and is incited somebody to action
It is cooled to -25 DEG C.Then at -25 DEG C, be slowly added dropwise thereto o- dimethylamino benzyl lithium (0.62g, Fw=141.14,
Toluene solution 4.4mmol) allows it to be warmed to room temperature naturally after being added dropwise, and continues to be stirred to react 16 hours at room temperature, has
White precipitate generates.After reaction, be filtered to remove insoluble matter, gained filtrate extracts solvent under vacuum, be used in combination it is anhydrous just oneself
Alkane washs 2 times and obtains bright yellow solid product 0.996g (Fw=575.58), yield 86.5%.
Nuclear magnetic data:1H-NMR(600MHz,C6D6):1.74(s,4H),2.21(s,12H,N-Me),3.10(s,3H,N-
), Me 5.02 (s, 1H), 6.62 (m, 2H), 6.69 (t, 2H, J=6Hz), 6.86 (m, 2H), 6.92 (m, 1H), 7.06 (m, 1H),
7.28 (m, 5H), 7.42 (d, 1H, J=6Hz), 7.73 (d, 1H, J=6Hz), 7.89 (d, 1H, J=6Hz)
Embodiment 4
According to the synthesis for carrying out target compound with the identical method in embodiment 3 for preparing, the difference is that N- methyl
The synthesis of indeno [2,1-b] indyl dichloride yttrium intermediate product carries out in toluene solvant, drains THF to eliminate and is used in combination
The step of toluene extracts, simplifies preparation process, while also avoiding the use of a large amount of THF solvents.
Nuclear magnetic data:1H-NMR(600MHz,C6D6):1.74(s,4H),2.21(s,12H,N-Me),3.10(s,3H,N-
), Me 5.02 (s, 1H), 6.62 (m, 2H), 6.69 (t, 2H, J=6Hz), 6.86 (m, 2H), 6.92 (m, 1H), 7.06 (m, 1H),
7.28 (m, 5H), 7.42 (d, 1H, J=6Hz), 7.73 (d, 1H, J=6Hz), 7.89 (d, 1H, J=6Hz)
Embodiment 5
The anhydrous GdCl of 0.527g are weighed in Schlenk bottles of 100mL330mL tetrahydrochysenes are added in (Fw=263.61,2mmol)
Furans (through water removal), heating stirring 10 hours at 70 DEG C.Subsequent vacuum extracts THF, obtains white powdery solids GdCl3
(THF)n, it is directly used in next step.
Claim N- methyl indeno [2,1-b] indyl lithium salts 0.450g (Fw=225.21,2mmol) to be dissolved in anhydrous THF to be made
Solution.Then at -25 DEG C, it is slowly dropped to GdCl3(THF)nIn the THF suspensions of (2mmol), allowed after being added dropwise
It is warmed to room temperature naturally, and continues to be stirred to react 12 hours at room temperature.THF is extracted after the completion of reaction under vacuum, residue is used
Dry toluene extracts, and collects filtrate after suction filtration, and extract toluene under vacuum, and it is N- methyl indenos to obtain buff grease
[2,1-b] indyl dichloride gadolinium is directly used in next step.
Above-mentioned N- methyl indeno [2,1-b] indyl dichloride gadolinium intermediate product is dissolved in dry toluene wiring solution-forming and is incited somebody to action
It is cooled to -25 DEG C.Then at -25 DEG C, be slowly added dropwise thereto o- dimethylamino benzyl lithium (0.62g, Fw=141.14,
Toluene solution 4.4mmol) allows it to be warmed to room temperature naturally after being added dropwise, and continues to be stirred to react 16 hours at room temperature, has
White precipitate generates.After reaction, be filtered to remove insoluble matter, gained filtrate extracts solvent under vacuum, be used in combination it is anhydrous just oneself
Alkane washs 2 times and obtains product as light yellow solid 0.970g (Fw=643.92), yield 75.3%.
Embodiment 6
Weigh 1.15g N- methyl indeno [2,1-b] indoles (Fw=respectively in the Schlenk bottles of 2 100mL
219.28,5.25mmol) and 2.80g Gd (CH2C6H4NMe2-o)3(Fw=559.84,5mmol) is dissolved in respectively in 30mL toluene
Solution is made.At ambient temperature, the toluene solution (light brown) of N- methyl indeno [2,1-b] indoles is slowly added drop-wise to Gd
(CH2C6H4NMe2-o)3Toluene solution (faint yellow) in, then continue at room temperature stirring 1 hour.Then, reaction bulb is set
50 DEG C are heated in oil bath, and the reaction was continued 12 hours, reaction solution gradually becomes crocus from faint yellow.Reaction terminates
Afterwards, solvent is extracted under vacuum, obtains dark brown oil, 20mL n-hexanes are added, solid is precipitated, filtered and with a small amount of n-hexane
Buff powder solid 2.24g (Fw=643.92), yield 69.6% are obtained after washing 2 times.
Embodiment 7
The anhydrous YCl of 0.39g are weighed in Schlenk bottles of 100mL320mL tetrahydrochysene furans are added in (Fw=195.26,2mmol)
It mutters (through water removal), heating stirring 10 hours at 60 DEG C.Subsequent vacuum extracts THF, obtains white powdery solids YCl3
(THF)3.5, it is directly used in next step.
Claim N- phenyl indeno [2,1-b] indyl lithium salts 0.574g (Fw=287.28,2mmol) to be dissolved in anhydrous THF to be made
Solution.Then at -25 DEG C, it is slowly dropped to 0.96g GdCl3(THF)nIn the THF suspensions of (2mmol), drip
It allows it to be warmed to room temperature naturally after finishing, and continues to be stirred to react 12 hours at room temperature.THF is extracted under vacuum after the completion of reaction, is remained
Excess is extracted with dry toluene, filtrate is collected after suction filtration, and extract toluene under vacuum, and it is N- phenyl indenos to obtain yellow solid
[2,1-b] indyl dichloride yttrium is directly used in next step.
Above-mentioned N- phenyl indeno [2,1-b] indyl dichloride yttrium intermediate product is dissolved in dry toluene wiring solution-forming and is incited somebody to action
It is cooled to -25 DEG C.Then at -25 DEG C, be slowly added dropwise thereto o- dimethylamino benzyl lithium (0.62g, Fw=141.14,
Toluene solution 4.4mmol) allows it to be warmed to room temperature naturally after being added dropwise, and continues to be stirred to react 16 hours at room temperature, has
White precipitate generates.After reaction, be filtered to remove insoluble matter, gained filtrate extracts solvent under vacuum, be used in combination it is anhydrous just oneself
Alkane washs 2 times and obtains bright yellow solid product 1.06g (Fw=637.64), yield 83.1%.
Nuclear magnetic data:1H-NMR(600MHz,C6D6):1.85(s,4H),2.10(s,12H,N-Me),5.19(s,1H),
6.56(m,2H),6.68(m,2H),6.80(m,1H),6.91(m,1H),7.04(m,2H),7.22(m,7H),7.55(m,4H),
7.83(m,2H).
Embodiment 8
Weigh 1.48g N- phenyl indeno [2,1-b] indoles (Fw=respectively in the Schlenk bottles of 2 100mL
281.35,5.25mmol) and 2.46g Y (CH2C6H4NMe2-o)3(Fw=491.50,5mmol) is dissolved in respectively in 30mL toluene
Solution is made.At ambient temperature, the toluene solution (colourless) of N- phenyl indeno [2,1-b] indoles is slowly added drop-wise to Y
(CH2C6H4NMe2-o)3Toluene solution (faint yellow) in, then continue at room temperature stirring 1 hour.Then, reaction bulb is set
80 DEG C are heated in oil bath, and the reaction was continued 12 hours, reaction solution gradually becomes crocus from faint yellow.Reaction terminates
Afterwards, solvent is extracted under vacuum, obtains buff grease, 20mL n-hexanes are added, solid is precipitated, filtered and with a small amount of n-hexane
Glassy yellow powder solid 2.607g (Fw=637.64), yield 81.8% are obtained after washing 2 times.
Nuclear magnetic data:1H-NMR(600MHz,C6D6):1.85(s,4H),2.10(s,12H,N-Me),5.19(s,1H),
6.56(m,2H),6.68(m,2H),6.80(m,1H),6.91(m,1H),7.04(m,2H),7.22(m,7H),7.55(m,4H),
7.83(m,2H).
Embodiment 9
The anhydrous GdCl of 0.526g are weighed in Schlenk bottles of 100mL330mL tetrahydrochysenes are added in (Fw=263.61,2mmol)
Furans (through water removal), heating stirring 10 hours at 70 DEG C.Subsequent vacuum extracts THF, obtains white powdery solids GdCl3
(THF)3, it is directly used in next step.
N- phenyl indeno [2,1-b] indyl lithium salts 0.574g (Fw=287.28,2mmol) be dissolved in anhydrous THF be made it is molten
Liquid.Then at -25 DEG C, it is slowly dropped to 0.96g GdCl3(THF)3In the THF suspensions of (2mmol), it is added dropwise
After allow it to be warmed to room temperature naturally, and continue to be stirred to react 12 hours at room temperature.THF is extracted under vacuum after the completion of reaction, it is remaining
Object is extracted with dry toluene, filtrate is collected after suction filtration, and extract toluene under vacuum, and it is N- phenyl indenos to obtain yellow oil
[2,1-b] indyl dichloride gadolinium is directly used in next step.
Above-mentioned N- phenyl indeno [2,1-b] indyl dichloride gadolinium intermediate product is dissolved in dry toluene wiring solution-forming and is incited somebody to action
It is cooled to -25 DEG C.Then at -25 DEG C, be slowly added dropwise thereto o- dimethylamino benzyl lithium (0.62g, Fw=141.14,
Toluene solution 4.4mmol) allows it to be warmed to room temperature naturally after being added dropwise, and continues to be stirred to react 16 hours at room temperature, has
White precipitate generates.After reaction, be filtered to remove insoluble matter, gained filtrate extracts solvent under vacuum, be used in combination it is anhydrous just oneself
Alkane washs 2 times and obtains bright yellow solid product 1.088g (Fw=705.99), yield 77.1%.
Embodiment 10
The anhydrous NdBr of 0.768g are weighed in Schlenk bottles of 100mL330mL tetrahydrochysenes are added in (Fw=383.95,2mmol)
Furans (through water removal), heating stirring 10 hours at 70 DEG C.Subsequent vacuum extracts THF, obtains white powdery solids NdBr3
(THF)n, it is directly used in next step.
N- phenyl indeno [2,1-b] indyl lithium salts 0.574g (Fw=287.28,2mmol) be dissolved in anhydrous THF be made it is molten
Liquid.Then at -25 DEG C, it is slowly dropped to NdBr3(THF)nIn the THF suspensions of (2mmol), it is allowed after being added dropwise
Naturally it is warmed to room temperature, and continues to be stirred to react 12 hours at room temperature.THF, residue nothing are extracted after the completion of reaction under vacuum
Water-toluene extracts, and collects filtrate after suction filtration, and extract toluene under vacuum, and it is N- phenyl indeno [2,1- to obtain brown oil
B] indyl dibrominated neodymium, it is directly used in next step.
Above-mentioned N- phenyl indeno [2,1-b] indyl dibrominated neodymium intermediate product is dissolved in dry toluene wiring solution-forming and is incited somebody to action
It is cooled to -25 DEG C.Then at -25 DEG C, be slowly added dropwise thereto o- dimethylamino benzyl lithium (0.62g, Fw=141.14,
Toluene solution 4.4mmol) allows it to be warmed to room temperature naturally after being added dropwise, and continues to be stirred to react 16 hours at room temperature, has
White precipitate generates.After reaction, be filtered to remove insoluble matter, gained filtrate extracts solvent under vacuum, be used in combination it is anhydrous just oneself
Alkane washs 2 times and obtains brown solid product 1.048g (Fw=692.98), yield 75.6%.
Embodiment 11
The anhydrous SmCl of 0.513g are weighed in Schlenk bottles of 100mL330mL tetrahydrochysenes are added in (Fw=256.72,2mmol)
Furans (through water removal), heating stirring 10 hours at 70 DEG C.Subsequent vacuum extracts THF, obtains white powdery solids SmCl3
(THF)n, it is directly used in next step.
Claim N- phenyl indeno [2,1-b] indyl lithium salts 0.574g (Fw=287.28,2mmol) to be dissolved in anhydrous THF to be made
Solution.Then at -25 DEG C, it is slowly dropped to SmCl3(THF)nIn the THF suspensions of (2mmol), allowed after being added dropwise
It is warmed to room temperature naturally, and continues to be stirred to react 12 hours at room temperature.THF is extracted after the completion of reaction under vacuum, residue is used
Dry toluene extracts, and collects filtrate after suction filtration, and extract toluene under vacuum, obtain brown oil be N- phenyl indeno [2,
1-b] indyl dichloride shirt, it is directly used in next step.
Above-mentioned N- phenyl indeno [2,1-b] indyl dichloride shirt intermediate product is dissolved in dry toluene wiring solution-forming and is incited somebody to action
It is cooled to -25 DEG C.Then at -25 DEG C, be slowly added dropwise thereto o- dimethylamino benzyl lithium (0.62g, Fw=141.14,
Toluene solution 4.4mmol) allows it to be warmed to room temperature naturally after being added dropwise, and continues to be stirred to react 16 hours at room temperature, has
White precipitate generates.After reaction, be filtered to remove insoluble matter, gained filtrate extracts solvent under vacuum, be used in combination it is anhydrous just oneself
Alkane washs 2 times and obtains brown solid 1.237g (Fw=699.10), yield 88.5%.
Embodiment 12
The anhydrous PrCl of 0.495g are weighed in Schlenk bottles of 100mL330mL tetrahydrochysenes are added in (Fw=247.27,2mmol)
Furans (through water removal), heating stirring 10 hours at 70 DEG C.Subsequent vacuum extracts THF, obtains white powdery solids PrCl3
(THF)n, it is directly used in next step.
Claim N- phenyl indeno [2,1-b] indyl lithium salts 0.574g (Fw=287.28,2mmol) to be dissolved in anhydrous THF to be made
Solution.Then at -25 DEG C, it is slowly dropped to PrCl3(THF)nIn the THF suspensions of (2mmol), allowed after being added dropwise
It is warmed to room temperature naturally, and continues to be stirred to react 12 hours at room temperature.THF is extracted after the completion of reaction under vacuum, residue is used
Dry toluene extracts, and collects filtrate after suction filtration, and extract toluene under vacuum, obtain brown oil be N- phenyl indeno [2,
1-b] indyl dichloride praseodymium, it is directly used in next step.
Above-mentioned N- phenyl indeno [2,1-b] indyl dichloride praseodymium intermediate product is dissolved in dry toluene wiring solution-forming and is incited somebody to action
It is cooled to -25 DEG C.Then at -25 DEG C, be slowly added dropwise thereto o- dimethylamino benzyl lithium (0.62g, Fw=141.14,
Toluene solution 4.4mmol) allows it to be warmed to room temperature naturally after being added dropwise, and continues to be stirred to react 16 hours at room temperature, has
White precipitate generates.After reaction, be filtered to remove insoluble matter, gained filtrate extracts solvent under vacuum, be used in combination it is anhydrous just oneself
Alkane washs 2 times and obtains bright yellow solid product 1.117g (Fw=689.65), yield 81.0%.
Embodiment 13
In inert atmosphere glove box, the hexane solution (mass fraction of 1,3-butadiene is weighed into 100mL round-bottomed flasks
15%) the hexane solution 0.2mL (1M, 0.2mmol) of triisobutyl aluminium is added in 14.4g (2.16g, 40mmol), and at room temperature
30min is stirred, the toluene that the complex (12mg, Fw=575.58,0.02mmol) of embodiment 4 is added into polymeric solution is molten
Liquid, and 1min is stirred, it is eventually adding [PhNHMe2][B(C6F5)4] (19mg, Fw=801.22,0.024mmol) toluene suspension
Liquid.After polymerizeing 1h at room temperature, polymerization system becomes viscous, and polymerized monomer completely consumes.After the completion of polymerization, reaction bulb is removed into inertia
Atmosphere glove box, be slowly added under stirring absolute methanol until polymer be precipitated completely, be added BHT antioxidant 0.02g (polymer
The 1% of quality), with absolute methanol washing copolymer 3 times, it is placed in vacuum drying oven and dries 5 hours for 70 DEG C, weigh.Unit interval
Turn over number (TOF) is 2667/h-1, cis--Isosorbide-5-Nitrae content is 92%.
Embodiment 14
Vinyl polymerization is carried out according to the identical method with embodiment 13, the difference is that using the cooperation of embodiment 6
Object.Unit interval turn over number (TOF) is 1013/h-1, cis--Isosorbide-5-Nitrae content is 91%.
Embodiment 15
Vinyl polymerization is carried out according to the identical method with embodiment 13, the difference is that mole of monomer and catalyst
Ratio is 10000.Unit interval turn over number (TOF) is 4000/h-1, cis--Isosorbide-5-Nitrae content is 93%.
As described above, indeno [2,1-b] indyl rare earth metal complex made from method provided by the invention is suitable for
The preparation of high-cis olefin rubber.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (15)
1. a kind of indeno [2,1-b] indyl rare earth metal complex, which is characterized in that indicated by following below formula [I]:
Wherein, Ln is the transition metal element of Group IIIB;
Z1And Z2It is identical or different, it is respectively selected from protium, halogen, alkyl-R, silylation-SiR each independently3, alcoxyl
Base-OR, sulfydryl-SR, carboxyl-OCOR, amido-NR2With phosphino--PR2In one kind, wherein R is selected from by the full of C1-C20
With alkyl, the unsaturated alkenyl of C2-C20, the naphthenic base of C3-C20, the aryl or aralkyl of C6-C30 and its derivative, C1-
C30's contains group III A in the periodic table of elements to the heteroatomic alkyl of V Group IIA element, aryl or aralkyl and its derivative
One kind in the formed group of object;
DnFor the neutral ligand being coordinated with Ln, and n is the integer more than or equal to 0;
L is by the removing of chemical formula [II] compound and R6Hydrogen on connected carbon atom is formed by substituent group:
Wherein, R1To R10It is identical or different, it is respectively selected from each independently by hydrogen, halogen, the saturated alkyl of C1-C20, C2-C20
Unsaturated alkenyl, the naphthenic base of C3-C20, the aryl of C6-C30 and its derivative, C7-C30 aralkyl and its derivative, C1-
C30's contains group III A in the periodic table of elements to the heteroatomic alkyl of V Group IIA element, aryl or aralkyl and its derivative
One kind in the formed group of object, and R2To R5In and R7To R10In have at least two adjacent groups can be by being connected to
Substituted or unsubstituted aliphatic ring or aromatic ring are formed together.
2. indeno [2,1-b] indyl rare earth metal complex according to claim 1, which is characterized in that the Ln choosings
One kind from scandium, yttrium and lanthanide rare metallic element.
3. indeno [2,1-b] indyl rare earth metal complex according to claim 1, which is characterized in that Z1And Z2Respectively
Independently selected from trimethylsilyl methyl, two (trimethyl silyl) methyl, three (trimethyl silyl) methyl,
O- (N, N- dimethylamino) benzyl, N, one kind in N- bis- (trimethyl silyl) amido.
4. indeno [2,1-b] indyl rare earth metal complex according to claim 1, which is characterized in that the C1-
The saturated alkyl of C20 is selected from methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, amyl, hexyl, heptyl, pungent
One kind in base;The unsaturated alkenyl of the C2-C20 in vinyl, acrylic, allyl, cyclobutenyl, pentenyl one
Kind;The one kind of the naphthenic base of the C3-C20 in cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl;The aryl of the C6-C30
And its one kind of derivative in phenyl, xenyl, naphthalene, phenanthryl, fluorenyl;The aralkyl and its derivative of the C7-C30
Selected from benzyl, p-methylphenyl, o-methyl-phenyl, aminomethyl phenyl, adjacent 3,5-dimethylphenyl, 3,5-dimethylphenyl, equal trimethyl
Phenyl, adjacent diisopropyl phenyl, to one kind in tert-butyl-phenyl;The C1-C30's contains group III A in the periodic table of elements
To the heteroatomic alkyl of V Group IIA, aryl, aralkyl and its derivative be selected from chloromethyl, bromomethyl, iodomethyl, chloroethyl,
Bromoethyl, iodine ethyl, trimethyl silyl, triethylsilyl, tripropylsilyl base, tributylsilyl, three
Isopropyl silyl, trimethylsilyl methyl, dimethylamino, diethylin, diisopropyl amido, methoxyl group, ethoxy
Base, cyano, nitro, trifluoromethyl, p-fluorophenyl, rubigan, p-bromophenyl, p-trifluoromethyl phenyl, p-methoxyphenyl,
To cyano-phenyl, p-nitrophenyl, to one kind in dimethylaminophenyl.
5. indeno [2,1-b] indyl rare earth metal complex according to claim 1, which is characterized in that DnSelected from tetrahydrochysene
One kind in furans, ether, thiophene, pyridine, pyrroles, imidazoles, carbazole, oxazole, triphenylphosphine.
6. a kind of preparation method of indeno [2,1-b] indyl rare earth metal complex, is described in claim any one of 1-5
Complex preparation method, which is characterized in that include the following steps:
By chemical formula [II] compound and with trisubstituted rare earth compound LnZ3After heating, it is made by acid-base reaction
Indeno [2,1-b] indyl rare earth metal complex of the Dan Mao;
Above-mentioned acid-base reaction carries out in reaction dissolvent;
LnZ3In, Ln is the transition metal element of Group IIIB;
Z is selected from protium, halogen, alkyl-R, silylation-SiR3, alkoxy-OR, sulfydryl-SR, carboxyl-OCOR, amine
Base-NR2With phosphino--PR2In one kind, wherein R is selected from by unsaturated alkenyl, the C3- of the saturated alkyl of C1-C20, C2-C20
The naphthenic base of C20, the aryl or aralkyl of C6-C30 and its derivative, C1-C30 are arrived containing group III A in the periodic table of elements
One kind in the heteroatomic alkyl of V Group IIA element, aryl or aralkyl and its formed group of derivative;
Chemical formula [II] compound is as follows:
Wherein, R1To R10It is identical or different, it is respectively selected from each independently by hydrogen, halogen, the saturated alkyl of C1-C20, C2-C20
Unsaturated alkenyl, the naphthenic base of C3-C20, the aryl of C6-C30 and its derivative, C7-C30 aralkyl and its derivative, C1-
The heteroatomic alkyl of transition metal element element, aryl or aralkyl containing Group IIIB in the periodic table of elements of C30 and its
One kind in the formed group of derivative, and R2To R5In and R7To R10In at least two adjacent group can pass through
It links together and forms substituted or unsubstituted aliphatic ring or aromatic ring.
7. the preparation method of indeno [2,1-b] indyl rare earth metal complex according to claim 6, feature exist
In the reaction temperature of the acid-base reaction is 0 DEG C~120 DEG C.
8. the preparation method of indeno [2,1-b] indyl rare earth metal complex according to claim 6, feature exist
In, the Z be selected from trimethylsilyl methyl, two (trimethyl silyl) methyl, three (trimethyl silyl) methyl,
O- (N, N- dimethylamino) benzyl, N, one kind in N- bis- (trimethyl silyl) amido.
9. the preparation method of indeno [2,1-b] indyl rare earth metal complex according to claim 6, feature exist
In the reaction dissolvent is selected from least one of toluene, hexane, ether, tetrahydrofuran.
10. a kind of preparation method of indeno [2,1-b] indyl rare earth metal complex, is any one of claim 1-5 institutes
The preparation method for the complex stated, which is characterized in that include the following steps:
S1 carries out lithiation by alkyl lithium reagents and chemical formula [II] compound and obtains lithiated product;
S2 is by lithiated product and LnX3Carry out the double halogenations of indeno [2,1-b] indyl rare earth metal that Dan Mao is made in salt elimination reaction
Object;
The double halide of indeno [2,1-b] indyl rare earth metal of Dan Mao are carried out elimination reaction, system by S3 with nucleophilic displacement of fluorine reagent
Obtain indeno [2,1-b] the indyl rare earth metal complex;
Above-mentioned S1, S2 and S3 are carried out in organic solvent;
Wherein, chemical formula [II] compound is as follows:
Wherein, R1To R10It is identical or different, it is respectively selected from each independently by hydrogen, halogen, the saturated alkyl of C1-C20, C2-C20
Unsaturated alkenyl, the naphthenic base of C3-C20, the aryl of C6-C30 and its derivative, C7-C30 aralkyl and its derivative, C1-
The heteroatomic alkyl of transition metal element element, aryl or aralkyl containing Group IIIB in the periodic table of elements of C30 and its
One kind in the formed group of derivative, and R2To R5In and R7To R10In at least two adjacent group can pass through
It links together and forms substituted or unsubstituted aliphatic ring or aromatic ring;
LnX3Middle Ln is the transition metal element of Group IIIB;X is halogen.
11. the preparation method of indeno [2,1-b] indyl rare earth metal complex according to claim 10, feature exist
In X is chlorine, bromine or iodine.
12. the preparation method of indeno [2,1-b] indyl rare earth metal complex according to claim 10, feature exist
In the reaction temperature of the lithiation is -80 DEG C~25 DEG C;The reaction temperature of the salt elimination reaction is -80 DEG C~25 DEG C;
The reaction temperature of the elimination reaction is -80 DEG C~25 DEG C.
13. the preparation method of indeno [2,1-b] indyl rare earth metal complex according to claim 10, feature exist
In the alkyl lithium reagents are selected from least one of lithium methide, n-BuLi, tert-butyl lithium, lithium diisopropyl amido.
14. the preparation method of indeno [2,1-b] indyl rare earth metal complex according to claim 10, feature exist
In the nucleophilic displacement of fluorine reagent is selected from trimethylsilyl methyl lithium, two (trimethyl silyl) lithium methides, three (front threes
Base silicyl) lithium methide, o- (N, N- dimethylamino) benzyl lithium, N, in N- bis- (trimethyl silyl) amido lithium extremely
Few one kind.
15. the preparation method of indeno [2,1-b] indyl rare earth metal complex according to claim 10, feature exist
In the organic solvent is selected from least one of toluene, hexane, ether, tetrahydrofuran.
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