Economic and safe synthesis method of zero-valent nickel coordination compound

A coordination compound and synthesis method technology, applied in the field of synthesis of zero-valent nickel coordination compounds, can solve the problems of expensive raw materials, unfavorable industrialization, high risk factor, etc., and achieve high product yield and purity, safe and stable reaction, and dangerous reaction small effect

Pending Publication Date: 2021-01-01
安徽敦茂新材料科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Most of these zero-valent nickel complexes are sensitive to air and water, and are difficult to prepare and store. There are relatively few reports on their synthesis processes.
In the prior art, Chinese patent CN201911198237.4 discloses a method for preparing bis(1,5-cyclooctadiene) nickel, which uses divalent nickel acetylacetonate as the nickel source, and 1,5-cyclooctadiene Diisobutylaluminum hydride is prepared by reacting alkenes and diisobutylaluminum hydride at low temperature; in this method, a strong reducing agent of diisobutylaluminum hydride is used, which has a high risk factor and is not conducive to industrial production
Belderrain, Tomas R also discloses a kind of preparation method of bis(1,5-cyclooctadiene) nickel, is prepared by reacting with 1,5-cyclooctadiene and metal sodium with nickel pyridine chloride as nickel source The crude product was washed with methanol several times and recrystallized from hot toluene to obtain (Belderrain, Tomas R; Knight, D.Andrew; Irvine, Derek J; Poveda, Manuel L.Journal of the Chemical Society, Dalton Transactions, 1992, #9, p .1491-1496); This method kind has also adopted strong reductant metal sodium, and risk factor is high, and experimental operation is complicated, is unfavorable for suitability for industrialization
Materne, Karolin disclose a kind of preparation method of tetrakis (triphenylphosphine) nickel, use two (1,5-cyclooctadiene) nickels as nickel source, use tetrahydrofuran and diethyl ether mixed solvent system, add triphenylphosphine, The solvent was removed by vacuum, and the product was obtained by washing (Materne, Karolin; Christin; Braun-Cula, Beatrice; Limberg, Christian, Zeitschrift furAnorganische und Allgemeine Chemie, 2018, vol.644, #14, p.700-705); As a nickel source, the raw material itself is relatively expensive, and it is not conducive to industrial production

Method used

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  • Economic and safe synthesis method of zero-valent nickel coordination compound
  • Economic and safe synthesis method of zero-valent nickel coordination compound
  • Economic and safe synthesis method of zero-valent nickel coordination compound

Examples

Experimental program
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Effect test

Embodiment 1

[0020] Add 0.05 mol of nickel chloride hexahydrate into a 250 ml three-neck flask, add a polytetrafluoroethylene magnetic stirring bar, add 0.2 mol of trimethylphosphine, and add 50 ml of tetrahydrofuran. React at room temperature under argon protection, stir for 4 hours, add 6 g of dry molecular sieves, raise the temperature to 50°C and stir for 30 minutes, stir to return to room temperature, add 0.025mol zinc powder, and react for 1 hour. Under the protection of argon, add an appropriate amount of diatomaceous earth dried at 100°C to the funnel, and filter it. The filtrate is vacuum-removed, washed with an appropriate amount of methanol, recrystallized by n-hexane, filtered, and the solid is vacuum-dried to obtain 16.5 g of yellow The solid, ie tetrakis(trimethylphosphine)nickel, has a yield of 91% and a purity of 99%.

[0021] The resulting product is used as a proton nuclear magnetic resonance spectrum and a phosphorus nuclear magnetic resonance spectrum, and the spectrogr...

Embodiment 2

[0023] Add 0.05mol nickel chloride hexahydrate into a 250ml three-necked flask, add a polytetrafluoroethylene magnetic stirring bar, add 0.1mol 1,5-cyclooctadiene, and add 50ml tetrahydrofuran. Reaction at room temperature, protected by argon, stirring for 4.5 hours, adding 6g of dry molecular sieves, raising the temperature to 40°C and stirring for 40 minutes, stirring to return to room temperature, adding 0.025mol zinc powder, and reacting for 1.5 hours. Under the protection of argon, add an appropriate amount of diatomaceous earth dried at 100°C to the funnel, filter, remove the solvent in the filtrate, wash with an appropriate amount of methanol, recrystallize through n-hexane, filter, and dry the solid in vacuum to obtain 12.7 g of Yellow solid, ie bis(1,5-cyclooctadiene)nickel, with a yield of 92.4% and a purity of 99%.

[0024] Gained product is done proton nuclear magnetic resonance spectrum, spectrogram sees image 3 , H1 NMR (400MHz, C 6 D. 6 ): δ4.30(s,8H,8CH),2....

Embodiment 3

[0026] Add 0.05 mol of nickel chloride hexahydrate into a 250 ml three-necked flask, add a polytetrafluoroethylene magnetic stirring bar, add 0.2 mol of triphenylphosphine, and add 50 ml of tetrahydrofuran. Reaction at room temperature, protected by argon, stirring for 5 hours, adding 6 g of dry molecular sieves, raising the temperature to 80°C and stirring for 20 minutes, stirring to return to room temperature, adding 0.025mol zinc powder, and reacting for 2 hours. Under the protection of argon, add an appropriate amount of diatomaceous earth dried at 100°C to the funnel, and filter it. The filtrate is vacuum-removed, washed with an appropriate amount of methanol, recrystallized by n-hexane, filtered, and the solid is vacuum-dried to obtain 51 g of yellow-brown The solid, ie tetrakis(trimethylphosphine)nickel, has a yield of 92% and a purity of 99%.

[0027] The resulting product was subjected to Elemental analysis: C: 78.04, H: 5.48, Ni: 5.36, P: 11.12.

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Abstract

The invention discloses an economic and safe synthesis method of a zero-valent nickel coordination compound, and relates to the technical field of medical catalysis. The structural formula of the zero-valent nickel coordination compound is NiRn, wherein the valence state of Ni is zero, R is a coordination ligand, n is the coordination number. The synthesis method comprises the following steps: adding tetrahydrofuran, nickel chloride hexahydrate and the coordination ligand to a reactor, stirring to react under the protection of inert gas, adding a molecular sieve, heating, stirring to react, cooling, adding zinc powder, and stirring to react; and after the reaction is finished, filtering the reaction system under the protection of inert gas, drying in vacuum to remove the organic solvent, washing, recrystallizing, and drying in vacuum to obtain the product. The method has the advantages of simple process operation, cheap and easily available raw materials, safe and stable reaction, highefficiency, high yield and high purity, and can be used for preparing several common zero-valent nickel coordination compounds.

Description

technical field [0001] The invention relates to the technical field of medical catalysis, in particular to an economical and safe synthesis method of a zero-valent nickel coordination compound. Background technique [0002] Zero-valent nickel coordination compound, also known as bare nickel or ligand-free nickel, is a π-olefin complex of nickel. Such as bis(1,5-cyclooctadiene) nickel, tetrakis(triphenylphosphine) nickel, etc. From a formal point of view, zero-valent nickel means that the oxidation state of nickel is zero, and nickel is not oxidized or reduced by ene ligands, which provide lone electrons, so that the effective atomic number of nickel reaches a stable electronic configuration. The zero-valent nickel complex is very active, and its ligands are easily replaced by other hydrocarbon ligands, especially dienes and trienes can be interchanged with each other. Therefore, this kind of material has good catalytic activity, high mechanical strength and good thermal co...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/04C07F9/50
CPCC07F15/04C07F9/5045C07F9/505C07F9/5095
Inventor 曾超张庆平姚瑞
Owner 安徽敦茂新材料科技有限公司
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