Metal complex using pyridine as matrix and synthetic method thereof

Abstract

The invention provides a metallic complex taking pyridine as parent body. It comprises following steps: taking picoline as raw material, placing trimethyl silicon base on substituent group after modification, carrying out addition reaction with benzenenitrile and getting a kind of metallic organic compound complexed witheta3-aza and pyridine. The method is characterized by temperate reaction condition, simple process, fast reaction speed and high productivity. The complex can be used as catalyst for alkene polymerization, and is characterized by long endurance, low cost, stable performance for oxygen atom and other foreign atoms in functional group, high activity and adjustable selectivity.

Description

technical field

[0001] The invention relates to a metal organic compound, in particular to a metal complex with a substituted pyridine as a parent and a synthesis method thereof. The metal complex can be used as an olefin polymerization catalyst. Background technique

[0002] Complexes containing pyridine functional groups have aroused great interest in recent years. These metal complexes have unusual three-dimensional configurations and different forms of bonding modes. The catalytic experiments of olefin polymerization have proved to have very good catalytic effects. They can be used as Olefin polymerization catalysts.

[0003] The research work of olefin polymerization catalysts has always attracted the attention of chemists. In 1957, Italian Montecatini Company realized the industrialization of propylene polymerization, which made the general resin industry develop rapidly (Ziegler, K., Breil, H., Martion, H., Holzkamp, ​​R., DE, 973 626, 1953, 11, 17 ; Natta, G, Pino,...

Examples

Embodiment 1

[0024] Example 1: Co[C 5 h 4 NCHC(Ph)NSiMe 3 ] 2 preparation of

[0025] Take 2-picoline (2.569g, 27.59mmol) in a Schlenk bottle, add about 30ml of ether to dissolve it. At 0°C, an equimolar amount of n-butyllithium (9.5ml, 27.59mmol) was added thereto, the color of the solution turned red, and after returning to room temperature, stirred for 4 hours to obtain compound (C 5 h 4 NCH 2 ) Li. At 0°C, continue to add an equimolar amount of trimethylchlorosilane (3.49ml, 27.59mmol) to the solution, and after returning to room temperature, stir for 4 hours to obtain a yellow turbid solution, which is left to stand and filtered to obtain compound C 5 h 4 NCH 2 SiMe 3 light yellow solution. The calculated yield is 93%.

[0026] Under ice-bath cooling conditions, take n-butyllithium (8.8ml, 25.66mmol), add the C obtained above 5 h 4 NCH 2 SiMe 3 In the solution, the solution turned dark red, and after returning to room temperature, stirred for 4 hours to obtain the comp...

Embodiment 2

[0036] Embodiment 2: [C 5 h 4 NCHC(Ph)NSiMe 3 ]SnCl 3 preparation of

[0037] Take η 3 - Azaallyl ligand compound (1) (1.234g, 4.5mmol), add about 10ml of ether solvent, slowly add SnCl dropwise to it at -78°C 4 (0.53ml, 4.5mmol), the solution turned into a yellow turbid liquid, and after returning to room temperature for 12 hours, the solvent was removed under reduced pressure, and CH 2 Cl 2 Extract, filter, concentrate the filtrate, put it at room temperature to crystallize, and after 3 days, a yellow regular crystal compound [C 5 h 4 NCHC(Ph)NSiMe 3 ]SnCl 3 , (1.728g, 78%). 1 H NMR (300Hz, 298K, CDCl 3 ): δ (ppm) 0.14 (s, 9H, SiMe 3 ), 5.97(s, 1H, CH), 7.20-7.86(8H, Py and Ph), 8.96(d, 1H, Py). 13 C NMR (75MHz, 298K, CDCl 3 ): δ (ppm) 3.14 (SiMe 3 ), 106.63(CH), 120.48-161.29(Py, C=N andPh). Its molecular structure is as follows:

[0038]

[0039] [C 5 h 4 NCHC(Ph)NSiMe 3 ]SnCl 3 molecular structure

[0040] [C 5 h 4 NCHC(Ph)NSiMe 3 ]SnCl 3 Part ...

Embodiment 3

[0045] Embodiment 3: [C 5 h 4 NCHC(Ph)NSiMe 3 ]GeCl 3 preparation of

[0046] Take crystal compound 1 (0.745g, 2.75mmol), add about 10mlEt 2 O diethyl ether solvent, slowly drop GeCl into it at -78°C 4 (0.31ml, 2.75mmol), the solution turned into an orange turbid liquid, after returning to room temperature, reacted for 12 hours, the solvent was removed under reduced pressure, and CH 2 Cl 2 Extract, filter, concentrate the filtrate, put it at room temperature to crystallize, and after 3 days, yellow blocky crystals appear [C 5 h 4 NCHC(Ph)NSiMe 3 ]GeCl 3 , (0.994g, 81%). 1 H NMR (300Hz, 298K, CDCl 3 ): δ (ppm) 0.053-0.22 (SiMe 3 ), 5.70 (CH), 7.10-7.77 (Py and Ph), 8.79 (Py).

technical field

[0001] The invention relates to a metal organic compound, in particular to a metal complex with a substituted pyridine as a parent and a synthesis method thereof. The metal complex can be used as an olefin polymerization catalyst. Background technique

[0002] Complexes containing pyridine functional groups have aroused great interest in recent years. These metal complexes have unusual three-dimensional configurations and different forms of bonding modes. The catalytic experiments of olefin polymerization have proved to have very good catalytic effects. They can be used as Olefin polymerization catalysts.

[0003] The research work of olefin polymerization catalysts has always attracted the attention of chemists. In 1957, Italian Montecatini Company realized the industrialization of propylene polymerization, which made the general resin industry develop rapidly (Ziegler, K., Breil, H., Martion, H., Holzkamp, ​​R., DE, 973 626, 1953, 11, 17 ; Natta, G, Pino,...

Examples

Embodiment 1

[0024] Example 1: Co[C 5 h 4 NCHC(Ph)NSiMe 3 ] 2 preparation of

[0025] Take 2-picoline (2.569g, 27.59mmol) in a Schlenk bottle, add about 30ml of ether to dissolve it. At 0°C, an equimolar amount of n-butyllithium (9.5ml, 27.59mmol) was added thereto, the color of the solution turned red, and after returning to room temperature, stirred for 4 hours to obtain compound (C 5 h 4 NCH 2 ) Li. At 0°C, continue to add an equimolar amount of trimethylchlorosilane (3.49ml, 27.59mmol) to the solution, and after returning to room temperature, stir for 4 hours to obtain a yellow turbid solution, which is left to stand and filtered to obtain compound C 5 h 4 NCH 2 SiMe 3 light yellow solution. The calculated yield is 93%.

[0026] Under ice-bath cooling conditions, take n-butyllithium (8.8ml, 25.66mmol), add the C obtained above 5 h 4 NCH 2 SiMe 3 In the solution, the solution turned dark red, and after returning to room temperature, stirred for 4 hours to obtain the comp...

Embodiment 2

[0036] Embodiment 2: [C 5 h 4 NCHC(Ph)NSiMe 3 ]SnCl 3 preparation of

[0037] Take η 3 - Azaallyl ligand compound (1) (1.234g, 4.5mmol), add about 10ml of ether solvent, slowly add SnCl dropwise to it at -78°C 4 (0.53ml, 4.5mmol), the solution turned into a yellow turbid liquid, and after returning to room temperature for 12 hours, the solvent was removed under reduced pressure, and CH 2 Cl 2 Extract, filter, concentrate the filtrate, put it at room temperature to crystallize, and after 3 days, a yellow regular crystal compound [C 5 h 4 NCHC(Ph)NSiMe 3 ]SnCl 3 , (1.728g, 78%). 1 H NMR (300Hz, 298K, CDCl 3 ): δ (ppm) 0.14 (s, 9H, SiMe 3 ), 5.97(s, 1H, CH), 7.20-7.86(8H, Py and Ph), 8.96(d, 1H, Py). 13 C NMR (75MHz, 298K, CDCl 3 ): δ (ppm) 3.14 (SiMe 3 ), 106.63(CH), 120.48-161.29(Py, C=N andPh). Its molecular structure is as follows:

[0038]

[0039] [C 5 h 4 NCHC(Ph)NSiMe 3 ]SnCl 3 molecular structure

[0040] [C 5 h 4 NCHC(Ph)NSiMe 3 ]SnCl 3 Part ...

Embodiment 3

[0045] Embodiment 3: [C 5 h 4 NCHC(Ph)NSiMe 3 ]GeCl 3 preparation of

[0046] Take crystal compound 1 (0.745g, 2.75mmol), add about 10mlEt 2 O diethyl ether solvent, slowly drop GeCl into it at -78°C 4 (0.31ml, 2.75mmol), the solution turned into an orange turbid liquid, after returning to room temperature, reacted for 12 hours, the solvent was removed under reduced pressure, and CH 2 Cl 2 Extract, filter, concentrate the filtrate, put it at room temperature to crystallize, and after 3 days, yellow blocky crystals appear [C 5 h 4 NCHC(Ph)NSiMe 3 ]GeCl 3 , (0.994g, 81%). 1 H NMR (300Hz, 298K, CDCl 3 ): δ (ppm) 0.053-0.22 (SiMe 3 ), 5.70 (CH), 7.10-7.77 (Py and Ph), 8.79 (Py).

Images