CN105254786A - C-C bridged [ONNO]-beta-ketoimine metal catalyst and preparation method thereof - Google Patents
C-C bridged [ONNO]-beta-ketoimine metal catalyst and preparation method thereof Download PDFInfo
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Abstract
A kind of C-C bridging [ONNO]-beta-ketimine metallic catalyst and preparation method, general structure are as follows:
Wherein, M=Ni, Pd, Co, Fe or Cu; R1, R2, R3 are corresponding alkyl. Preparation method includes: the preparation of (I) beta-ketimine ligand; (II) major catalyst C-C bridging [ONNO]-beta-ketimine metallic catalyst preparation. It is of the present invention that there is high light transmittance, high glass-transition temperature, good thermal stability, oxidation stability, low hydroscopicity, low dielectric constant and good processing, dissolution and adhesion property in the copolymer of catalyst norbornene and norbornene derivative.
Description
Technical field
The invention belongs to catalyzer and preparing technical field, particularly for Primary Catalysts and the preparation method of the catalyst system of the addition copolymerization of norbornylene and norbornene derivative.
Background technology
Along with industrial expansion, polycyclic olefin material relies on the performance of its excellence to obtain to pay close attention to widely.Norbornylene is a kind of typical cyclic olefin material, and it has three kinds of polymerization methodses: (1) ring-opening metathesis polymerization, containing double bond in the product main chain that this polymerization methods obtains, is a kind of polymerization methods of current most study; (2) positively charged ion or radical polymerization, this mode is connected by 2,7-position by monomer, but can only obtain the lower oligopolymer of molecular weight; (3) vinyl add-on type polymerization, this polymerization methods opens by double bond the addition polymerization carried out, containing twin nuclei (USPatent5468819,5569730) in main chain.Wherein the norbornylene homopolymer of add-on type has good optical property, thermostability, chemical stability, low rate of moisture absorption and specific inductivity, it is a kind of well polymer materials, but due to the crisp and processing characteristics of its matter and solubility property poor, so its application is in the industry greatly limited.It formerly advantageously improves that it is not enough simultaneously in reservation for our norbornylene of needing to prepare functionalization like this.
The optimization of catalyst system has vital meaning to raising functional poly norbornylene over-all properties, and the catalyst system therefore developing efficient stable is for very important development functional poly norbornylene.The Primary Catalysts mainly metal complexes of the catalyst system of catalysis norbornene polymerization, generally can be divided into Ziegler-Natta catalyst, metallocene catalyst, rear transition metal catalysis and rare-earth metal catalyst.Wherein the metal center of Ziegler-Natta catalyst and metallocene catalyst is early transition metal, poor to the tolerance of polar monomer, and the activity when catalysis polarity norbornene monomer is lower.Late transition metal catalyst is better to the tolerance of polar group, and synthesis is simple, higher to the catalytic activity of polarity norbornene monomer, is a kind of desirable catalyzer.In the development of late transition metal catalyst, we have done certain relevant work (Chinese Patent Application No.: 201110299869.7,201110299867.8).
Summary of the invention
The object of the present invention is to provide a kind of C-C bridging [ONNO]-beta-ketimine metal catalyst and preparation method, catalyzer of the present invention can be prepared and has high light transmittance, high glass-transition temperature, good thermostability, oxidative stability, low rate of moisture absorption, low specific inductivity and the norbornylene of good processing characteristics, solubility property and adhesion property and the multipolymer of norbornene derivative.
Catalyzer of the present invention is a kind of C-C bridging [ONNO]-beta-ketimine metal complexes, prepare by β-one with containing the aromatic amine of α-H and the prewired body of trans metal, possess unique C-C bridged linkage, and metal active centres is in [ONNO] four-coordination type.Catalyzer of the present invention mainly contains C-C bridging [ONNO]-beta-ketimine nickel (II), C-C bridging [ONNO]-beta-ketimine palladium (II), C-C bridging [ONNO]-beta-ketimine cobalt (II), C-C bridging [ONNO]-beta-ketimine iron (II) or C-C bridging [ONNO]-beta-ketimine copper (II) title complex etc.Its general structure is:
Wherein, M=Ni, Pd, Co, Fe or Cu.
R
1, R
2, R
3following situation can be respectively:
(1)R
1＝CH
3，R
2＝CH
3，R
3＝
(2)R
1＝CH
3，R
2＝CF
3，R
3＝
(3)R
1＝CH
3，R
2＝
R
3＝
(4)R
1＝CH
3，R
2＝CH
3，R
3＝
(5)R
1＝CH
3，R
2＝CF
3，R
3＝
(6)R
1＝CH
3，R
2＝
R
3＝
(7)R
1＝CH
3，R
2＝CH
3，R
3＝
(8)R
1＝CH
3，R
2＝CF
3，R
3＝
(9)R
1＝CH
3，R
2＝
R
3＝
(10)R
1＝CH
3，R
2＝CH
3，R
3＝
(11)R
1＝CH
3，R
2＝CF
3，R
3＝
(12)R
1＝CH
3，R
2＝
R
3＝
(13)R
1＝CH
2CH(CH
3)
2，R
2＝CH
3，R
3＝
(14)R
1＝CH
2CH(CH
3)
2，R
2＝CH
3，R
3＝
(15)R
1＝CH
2CH(CH
3)
2，R
2＝CH
3，R
3＝
(16)R
1＝CH
2CH(CH
3)
2，R
2＝CH
3，R
3＝
(17)R
1＝CF
3，R
2＝CF
3，R
3＝
(18)R
1＝CF
3，R
2＝
R
3＝
(19)R
1＝CF
3，R
2＝CF
3，R
3＝
(20)R
1＝CF
3，R
2＝
R
3＝
(21)R
1＝CF
3，R
2＝CF
3，R
3＝
(22)R
1＝CF
3，R
2＝
R
3＝
(23)R
1＝CF
3，R
2＝CF
3，R
3＝
(24)R
1＝CF
3，R
2＝
R
3＝
(25)R
1＝
R
2＝
R
3＝
(26)R
1＝
R
2＝
R
3＝
(27)R
1＝
R
2＝
R
3＝
(28)R
1＝
R
2＝
R
3＝
The preparation method of C-C bridging [ONNO]-beta-ketimine metal catalyst of the present invention, comprises the following steps:
(I) preparation of beta-ketimine part.
The beta-diketon that mol ratio is 1:1 and the aromatic amine containing α-H is added in the reaction flask that reflux condensing tube and water trap are housed, and the Glacial acetic acid of catalytic amount and 50-300mL ethanol, react after 8-48 hour, obtain with normal hexane recrystallization or underpressure distillation the beta-ketimine part that purity reaches more than 95%.
(II) preparation of Primary Catalysts C-C bridging [ONNO]-beta-ketimine metal catalyst.
Under nitrogen atmosphere, NaH is joined in tetrahydrofuran (THF) (THF) solution containing beta-ketimine part, the molar ratio of NaH and beta-ketimine part is 1:2, stirred at ambient temperature 4-8h, add the pre-part of trans metal of 1/2 equivalent afterwards, room temperature with constant stirs 8-12h, filter, recrystallization obtains C-C bridging [ONNO] beta-ketimine metal complexes.
Metal complexes as the activity of catalyzer, stability and selectivity mainly by the impact of its electronic effect and steric effect.Usually in its structure, strong electron-withdrawing group group is introduced to strengthen its electronic effect, as arene group etc.; And structure is found to strengthen steric effect in the space usually changing metal complexes, and then strengthen catalytic activity and the stability thereof of metal complexes, as introduced bridged group etc.The introducing of abutment improves the structural stability of bridging catalyzer, the group size of conversion abutment can regulate and control the steric hindrance in catalytic active center space, thus stereoselectivity when effectively regulating and controlling catalytic activity and polymerization, improve tacticity and the molecular weight of polymkeric substance.
The multipolymer of C-C bridging [ONNO] of the present invention-beta-ketimine metal catalyst catalysis norbornylene and norbornene derivative has high light transmittance, high glass-transition temperature, good thermostability, oxidative stability, low rate of moisture absorption, low specific inductivity and good processing characteristics, solubility property and adhesion property.
Accompanying drawing explanation
Fig. 1 is C-C bridging [ONNO] of the present invention-methyl ethyl diketone fluorenes imine nickel (II) single crystal structure figure.
Fig. 2 is C-C bridging [ONNO] of the present invention-trifluoroacetylacetone fluorenes imine nickel (II) single crystal structure figure.
Embodiment
The present invention will be described further by following examples.
Embodiment 1.
(I) preparation of methyl ethyl diketone fluorenes imine ligand.
9-aminofluorene hydrochloride (5.44g is added successively in a mouth bottle of 250ml, 0.025mol) and the ethanol solution of 100ml, stir till dissolving, at room temperature add triethylamine (2.54g, 0.025mol) and stir standing half hour after 2 hours.Supernatant liquor is transferred to methyl ethyl diketone (2.50g is housed, in ethanolic soln 0.025mol), add the Glacial acetic acid reflux 24 hours of 0.8mL again, with cold-trap, remaining solvent is taken away under vacuo, the solid of separating out carries out purifying in silicagel column n-hexane/ethyl acetate (50:1) as eluent, after purifying, in the mixed solvent of normal hexane and ethyl acetate, separate out yellow crystals, purity reaches 98%.
(II) synthesis of C-C bridging [ONNO]-methyl ethyl diketone fluorenes imine nickel (II) catalyzer.
The part (0.53g, 0.002mol) prepared by step I joins 100mL and is equipped with in a mouth bottle of magnetic stir bar, adds the THF that 40mL is dried under nitrogen protection condition, stirs and part is dissolved completely.Joined under nitrogen protection in mixed solution by NaH (0.144g, 0.006mol), solution colour becomes yellow-green colour.Under nitrogen atmosphere and normal temperature, vigorous stirring 4 hours, then all removes THF with cold-trap, obtains the mixed powder of grey.Under nitrogen protection; the dichloromethane solution that 15mL handles well is added in mixture; then glycol dimethyl ether nickelous bromide is added; stirred at ambient temperature is after 8 hours; filter with core filter bulb; collect filtrate, and carry out recrystallization, obtain bridging [ONNO]-methyl ethyl diketone fluorenes imine nickel (II) complex crystal.
1HNMR(CDCl
3,δ,ppm):1.92(s,6H,CH
3),2.23(s,6H,CH
3)，4.59(s,2H,CH),7.11-7.89(m,16H,C
13H
8).
13CNMR(CDCl
3,δ,ppm):17.21,25.23,64.40,127.61,131.23,134.32,140.36,143.68,147.82,150.73,169.54.Anal.Calc.forC
36H
30O
2N
2Ni:C,74.38；H,5.20；N,4.82.Found:C,74.40；H,5.19；N,4.79.
(III) application in norbornylene homopolymerization preparation.
With heat gun heating, magnetic stir bar and the reaction flask with a mouth are housed, it are vacuumized, inflated with nitrogen process simultaneously, replace three times, guarantee that reaction system is in dry nitrogen environment.In bottle, the toluene of 5-8mL is injected successively, the norbornylene toluene solution (ρ=0.4g/mL) of 1.2-2.4mL, the B (C of 1mL by syringe
6f
5)
3toluene solution (M=0.01
-10mol/L), the toluene solution of Primary Catalysts C-C bridging [ONNO]-methyl ethyl diketone fluorenes imine nickel (II) title complex of 1mL, react 30 minutes at 60 DEG C, then with 10% ethanol solution hydrochloride of 100mL, Primary Catalysts and promotor are decomposed, termination reaction, leave standstill 12 hours, by complete for polymkeric substance sedimentation.By sedimentation and filtration and at 40 DEG C in vacuum drying oven dry more than 24 hours to constant weight.Wherein the transformation efficiency of polymkeric substance is 75-100%, and catalytic activity is 1.02 × 10
6g
polymer/ mol
nih.
Embodiment 2.
(I) preparation of trifluoroacetylacetone fluorenamine part.
9-aminofluorene hydrochloride (5.44g is added successively in a mouth bottle of 250ml, 0.025mol) and the ethanol solution of 100ml, stir till dissolving, at room temperature add triethylamine (2.54g, 0.025mol) and stir standing half hour after 2 hours.Supernatant liquor is transferred in the ethanolic soln that trifluoroacetylacetone (4.25g, 0.025mol) is housed, then adds the Glacial acetic acid reflux 24 hours of 0.8mL.With cold-trap device, remaining solvent is taken away under vacuo, the solid of separating out carries out purifying in silicagel column n-hexane/ethyl acetate (50:1) as eluent, after purifying, in the mixed solvent of normal hexane and ethyl acetate, separate out yellow crystals, purity reaches 99%.
(II) synthesis of C-C bridging [ONNO]-trifluoroacetylacetone fluorenes imine nickel (II) catalyzer.
The part (0.67g, 0.002mol) prepared by step I joins 100mL and is equipped with in a mouth bottle of magnetic stir bar, adds the THF of 40mL drying under nitrogen protection condition, stirs and part is dissolved completely.Joined under nitrogen protection in mixed solution by NaH (0.144g, 0.004mol), solution colour becomes yellow-green colour.Under nitrogen atmosphere and normal temperature, vigorous stirring 4 hours, then all removes THF with cold-trap, obtains the mixed powder of white and grey.Under nitrogen protection; the dichloromethane solution that 15mL handles well is added in mixture; then glycol dimethyl ether nickelous bromide is added; stirred at ambient temperature is after 8 hours; filter with core filter bulb; collect filtrate, and carry out recrystallization, obtain C-C bridging [ONNO]-trifluoroacetylacetone fluorenes imine nickel (II) title complex green crystal.
1HNMR(CDCl
3,δ,ppm):1.36(s,6H,CH
3),5.33(s,2H,CH),7.09-7.16(m,16H,C
13H
8).
13CNMR(CDCl
3,δ,ppm):20.36,74.40,125.89,127.65,128.63,130.41,131.62,135.40,136.68,140.82,148.62,159.66,170.54.Anal.Calc.forC
36H
24O
2F
6N
2Ni:C,62.73；H,3.51；N,4.06.Found:C,62.75；H,3.48；N,4.09.
(III) application in norbornylene homopolymerization preparation.
With heat gun heating, magnetic stir bar and the reaction flask with a mouth are housed, it are vacuumized, inflated with nitrogen process simultaneously, replace three times, guarantee that reaction system is in dry nitrogen environment.In bottle, the toluene of 5-8mL is injected successively, the norbornylene toluene solution (ρ=0.4g/mL) of 1.2-2.4mL, the B (C of 1mL by syringe
6f
5)
3toluene solution (M=0.01
-10mol/L), Primary Catalysts C-C bridging [ONNO]-trifluoroacetylacetone fluorenes imine nickel (II) the title complex toluene solution of 1mL, react 30 minutes at 60 DEG C, then with 10% ethanol solution hydrochloride of 100mL, Primary Catalysts and promotor are decomposed, termination reaction, leave standstill 12 hours, by complete for polymkeric substance sedimentation.By sedimentation and filtration and at 40 DEG C in vacuum drying oven dry more than 24 hours to constant weight.Wherein the transformation efficiency of polymkeric substance is 80-100%, and catalytic activity is 1.2 × 10
6g
polymer/ mol
nih.
Embodiment 3.
(I) preparation of methyl ethyl diketone NSC 334072 part.
Benzhydrylamine (4.58g is added successively in a mouth bottle of 250ml, 0.025mol), methyl ethyl diketone (2.50g, 0.025mol) with 150mL ethanol, add the Glacial acetic acid reflux 24 hours of 0.8mL again, with cold-trap, remaining solvent is taken away under vacuo, the solid of separating out carries out purifying in silicagel column n-hexane/ethyl acetate (100:1) as eluent, after purifying, in the mixed solvent of normal hexane and ethyl acetate, separate out white crystal, purity reaches 99%.
(II) synthesis of C-C bridging [ONNO]-methyl ethyl diketone NSC 334072 palladium (II) catalyzer.
The part (0.53g, 0.002mol) prepared by step I joins 100mL and is equipped with in a mouth bottle of magnetic stir bar, adds the THF that 40mL is dried under nitrogen protection condition, stirs and part is dissolved completely.Joined under nitrogen protection in mixed solution by NaH (0.144g, 0.006mol), solution colour becomes brown color.Under nitrogen atmosphere and normal temperature, vigorous stirring 4 hours, then all removes THF with cold-trap, obtains linen mixed powder.Under nitrogen protection; the toluene solution that 15mL handles well is added in mixture; then add tetraethyl-amine tetrachloro and close sour palladium; stirred at ambient temperature is after 8 hours; filter with core filter bulb; collect filtrate, and carry out recrystallization, obtain bridging [ONNO]-methyl ethyl diketone NSC 334072 palladium (II) title complex red-brown crystals.
1HNMR(CDCl
3,δ,ppm):1.34(s,6H,CH
3),1.78(s,6H,CH
3)，4.12(s,2H,CH),4.65(s,2H,CH),7.12-7.33(m,20H,C
6H
5).
13CNMR(CDCl
3,δ,ppm):23.33,26.21,48.23,70.02,102.73,126.08,128.49,129.02,143.01,145.55.Anal.Calc.forC
36H
36O
2N
2Pd:C,68.08；H,5.71；N,4.41.Found:C,68.10；H,5.67；N,4.42.
(III) application in norbornylene homopolymerization preparation.
With heat gun heating, magnetic stir bar and the reaction flask with a mouth are housed, it are vacuumized, inflated with nitrogen process simultaneously, replace three times, guarantee that reaction system is in dry nitrogen environment.In bottle, the toluene of 5-8mL is injected successively, the norbornylene toluene solution (ρ=0.4g/mL) of 1.2-2.4mL, the B (C of 1mL by syringe
6f
5)
3toluene solution (M=0.01-10mol/L), the toluene solution of Primary Catalysts C-C bridging [ONNO]-methyl ethyl diketone NSC 334072 palladium (II) title complex of 1mL, react 30 minutes at 60 DEG C, then with 10% ethanol solution hydrochloride of 100mL, Primary Catalysts and promotor are decomposed, termination reaction, leave standstill 12 hours, by complete for polymkeric substance sedimentation.By sedimentation and filtration and at 40 DEG C in vacuum drying oven dry more than 24 hours to constant weight.Wherein the transformation efficiency of polymkeric substance is 90-100%, and catalytic activity is 0.97 × 10
6g
polymer/ mol
nih.
Embodiment 4.
(I) preparation of 1-benzoyl acetone benzyl imine ligand.
Benzylamine (2.7g is added successively in a mouth bottle of 250ml, 0.025mol), 1-benzoyl acetone (4.05g, 0.025mol) with 150mL ethanol, add the Glacial acetic acid reflux 24 hours of 0.8mL again, with cold-trap, remaining solvent is taken away under vacuo, the solid of separating out carries out purifying in silicagel column n-hexane/ethyl acetate (30:1) as eluent, after purifying, in the mixed solvent of normal hexane and ethyl acetate, separate out yellow crystals, purity reaches 95%.
(II) synthesis of C-C bridging [ONNO]-1-benzoyl acetone benzyl imines cobalt (II) catalyzer.
The part (0.502g, 0.002mol) prepared by step I joins 100mL and is equipped with in a mouth bottle of magnetic stir bar, adds the THF that 40mL is dried under nitrogen protection condition, stirs and part is dissolved completely.Joined under nitrogen protection in mixed solution by NaH (0.144g, 0.006mol), solution colour becomes brown color.Under nitrogen atmosphere and normal temperature, vigorous stirring 6 hours, then all removes THF with cold-trap, obtains deep yellow powder.Under nitrogen protection; the toluene solution that 15mL handles well is added in mixture; then cobalt chloride is added; stirred at ambient temperature is after 8 hours; filter with core filter bulb; collect filtrate, and carry out recrystallization, obtain bridging [ONNO]-1-benzoyl acetone benzyl imines cobalt (II) title complex scarlet crystal.
1HNMR(CDCl
3,δ,ppm):1.74(s,6H,CH
3),4.52(s,2H,CH)，4.89(s,2H,CH),5.17(s,2H,CH),7.09-7.24(m,20H,C
6H
5).
13CNMR(CDCl
3,δ,ppm):26.17,50.35,55.74,102.72,126.38,127.47,128.82,140.56,142.33,145.71.Anal.Calc.forC
34H
32O
2N
2Co:C,72.98；H,5.76；N,5.01.Found:C,72.79；H,5.84；N,4.92.
(III) application in norbornylene homopolymerization preparation.
With heat gun heating, magnetic stir bar and the reaction flask with a mouth are housed, it are vacuumized, inflated with nitrogen process simultaneously, replace three times, guarantee that reaction system is in dry nitrogen environment.In bottle, the toluene of 5-8mL is injected successively, the norbornylene toluene solution (ρ=0.4g/mL) of 1.2-2.4mL, the B (C of 1mL by syringe
6f
5)
3toluene solution (M=0.01-10mol/L), the toluene solution of Primary Catalysts C-C bridging [ONNO]-1-benzoyl acetone benzyl imines cobalt (II) title complex of 1mL, react 30 minutes at 60 DEG C, then with 10% ethanol solution hydrochloride of 100mL, Primary Catalysts and promotor are decomposed, termination reaction, leave standstill 12 hours, by complete for polymkeric substance sedimentation.By sedimentation and filtration and at 40 DEG C in vacuum drying oven dry more than 24 hours to constant weight.Wherein the transformation efficiency of polymkeric substance is 80-100%, and catalytic activity is 9.4 × 10
4g
polymer/ mol
nih.
Claims (2)
1. C-C bridging [ONNO]-beta-ketimine metal catalyst, its general structure is:
Wherein, M=Ni, Pd, Co, Fe or Cu;
R
1, R
2, R
3for:
(1)R
1＝CH
3，R
2＝CH
3，
(2)R
1＝CH
3，R
2＝CF
3，
(3)R
1＝CH
3，
(4)R
1＝CH
3，R
2＝CH
3，
(5)R
1＝CH
3，R
2＝CF
3，
(6)R
1＝CH
3，
(7)R
1＝CH
3，R
2＝CH
3，
(8)R
1＝CH
3，R
2＝CF
3，
(9)R
1＝CH
3，
(10)R
1＝CH
3，R
2＝CH
3，
(11)R
1＝CH
3，R
2＝CF
3，
(12)R
1＝CH
3，
(13)R
1＝CH
2CH(CH
3)
2，R
2＝CH
3，
(14)R
1＝CH
2CH(CH
3)
2，R
2＝CH
3，
(15)R
1＝CH
2CH(CH
3)
2，R
2＝CH
3，
(16)R
1＝CH
2CH(CH
3)
2，R
2＝CH
3，
(17)R
1＝CF
3，R
2＝CF
3，
(18)R
1＝CF
3，
(19)R
1＝CF
3，R
2＝CF
3，
(20)R
1＝CF
3，
(21)R
1＝CF
3，R
2＝CF
3，
(22)R
1＝CF
3，
(23)R
1＝CF
3，R
2＝CF
3，
(24)R
1＝CF
3，
(25)
(26)
(27)
(28)
2. the preparation method of C-C bridging [ONNO]-beta-ketimine metal catalyst according to claim 1, is characterized in that comprising the following steps:
(I) in the reaction flask that reflux condensing tube and water trap are housed, add the beta-diketon that mol ratio is 1:1 and the aromatic amine containing α-H, and the Glacial acetic acid of catalytic amount and 50-300mL ethanol, react after 8-48 hour, obtain beta-ketimine part with normal hexane recrystallization or underpressure distillation;
(II) under nitrogen atmosphere, NaH is joined in the tetrahydrofuran solution containing beta-ketimine part, the molar ratio of NaH and beta-ketimine part is 1:2, stirred at ambient temperature 4-8h, add the pre-part of trans metal of 1/2 equivalent afterwards, room temperature with constant stirs 8-12h, filter, recrystallization obtains C-C bridging [ONNO]-beta-ketimine metal complexes.
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| CN106543074A (en) * | 2016-10-10 | 2017-03-29 | 山东师范大学 | A kind of one-dimensional chiral Cu (II) chain coordination compound and preparation method and application |
| CN110423297A (en) * | 2019-08-05 | 2019-11-08 | 南昌大学 | Asymmetric transition-metal catalyst of a kind of [C^N^O] three tooth chelating and preparation method thereof |
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| CN106543074A (en) * | 2016-10-10 | 2017-03-29 | 山东师范大学 | A kind of one-dimensional chiral Cu (II) chain coordination compound and preparation method and application |
| CN106543074B (en) * | 2016-10-10 | 2019-03-19 | 山东师范大学 | One-dimensional chirality Cu (II) chain complex of one kind and the preparation method and application thereof |
| CN110423297A (en) * | 2019-08-05 | 2019-11-08 | 南昌大学 | Asymmetric transition-metal catalyst of a kind of [C^N^O] three tooth chelating and preparation method thereof |
| CN110423297B (en) * | 2019-08-05 | 2021-07-20 | 南昌大学 | [ C ^ N ^ O ] tridentate chelated asymmetric transition metal catalyst and preparation method thereof |
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