CN112159435A - Economic and safe synthesis method of zero-valent nickel coordination compound - Google Patents
Economic and safe synthesis method of zero-valent nickel coordination compound Download PDFInfo
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- CN112159435A CN112159435A CN202011082922.3A CN202011082922A CN112159435A CN 112159435 A CN112159435 A CN 112159435A CN 202011082922 A CN202011082922 A CN 202011082922A CN 112159435 A CN112159435 A CN 112159435A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/04—Nickel compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5095—Separation; Purification; Stabilisation
Abstract
The invention discloses an economic and safe synthesis method of a zero-valent nickel coordination compound, which relates to the technical field of medical catalysis, wherein the structural formula of the zero-valent nickel coordination compound is as follows: NiRnWherein, the valence state of Ni is zero, R is a coordination ligand, n is the coordination number, and the synthesis steps are as follows: adding tetrahydrofuran, nickel chloride hexahydrate and a coordination ligand into a reactor, stirring for reaction under the protection of inert gas, adding a molecular sieve, heating, stirring for reaction, cooling, adding zinc powder, and stirring for reaction; 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 obtained raw materials, safe and stable reaction, high efficiency and high yield and purity, and can be used for preparing several common zero-valent nickel coordination compounds.
Description
Technical Field
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
The zero-valent nickel coordination compound, also known as naked nickel or ligand free nickel, is a pi-olefin complex of nickel. Such as bis (1, 5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, etc. Formally, zero-valent nickel means that the oxidation state of nickel is zero, nickel is not oxidized or reduced by the alkene ligand, which provides lone electrons, bringing the effective atomic number of nickel to a stable electronic configuration. The zero-valent nickel complex is active and its ligands are readily displaced by other hydrocarbon ligands, particularly dienes and trienes, which are interchangeable with one another. Therefore, the substances have good catalytic activity, high mechanical strength and good thermal conductivity, can be used for catalyzing hydrogenation of various unsaturated hydrocarbons, and are good catalysts in certain conversion processes such as dehydrogenation, oxidative dehalogenation, desulfurization and the like, and are widely applied to petroleum, chemical engineering, pharmacy, grease, spice, hydrogen peroxide, synthetic fibers, particularly sorbitol, xylitol, maltitol and other industries.
Most of the zero-valent nickel coordination compounds are sensitive to air and water, are difficult to prepare and store, and have relatively few reports on the synthesis process. In the prior art, Chinese patent CN201911198237.4 discloses a preparation method of bis (1, 5-cyclooctadiene) nickel, which is prepared by taking divalent nickel acetylacetone nickel as a nickel source and reacting with 1, 5-cyclooctadiene and diisobutylaluminum hydride at low temperature; the method uses a strong diisobutylaluminum hydride reducing agent, has high danger coefficient, and is not beneficial to industrial production. Belderrain, Tomas R also discloses a process for preparing bis (1, 5-cyclooctadiene) nickel by reacting pyridine nickel chloride as a nickel source with 1, 5-cyclooctadiene and sodium metal to obtain a crude product, washing with methanol for a plurality of times, and recrystallizing with hot toluene to obtain (Belderrain, Tomas R; Knight, D.Andrew; Irvine, Derek J; Poveda, Manual L. journal of the Chemical Society, Dalton Transactions,1992, #9, p.1491-1496); the method also adopts strong reducing agent metal sodium, has high danger coefficient and complex experimental operation, and is not beneficial to industrialization. Materne, Karolin disclose a preparation method of tetrakis (triphenylphosphine) nickel, which uses bis (1, 5-cyclooctadiene) nickel as a nickel source, uses a mixed solvent system of tetrahydrofuran and diethyl ether, adds triphenylphosphine, removes the solvent through vacuum, and washes to obtain a product (Materne, Karolin;
christin; Braun-Cula, Beatrice; limberg, Christian, Zeitschrift fur inorganic algemeine Chemie,2018, vol.644, #14, p.700-705); in the method, bis (1, 5-cyclooctadiene) nickel is used as a nickel source and is used as a raw materialIs expensive and is not beneficial to industrial production.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides an economic and safe synthesis method of a zero-valent nickel coordination compound, the whole process is simple to operate, raw materials are cheap and easy to obtain, the reaction is safe and stable, the efficiency is high, and the yield and the purity are high.
The invention provides an economic and safe synthesis method of a zero-valent nickel coordination compound, wherein the structural formula of the zero-valent nickel coordination compound is as follows: NiRnWherein, the valence state of Ni is zero, R is a coordination ligand, n is the coordination number, and the synthesis steps are as follows: adding tetrahydrofuran, nickel chloride hexahydrate and a coordination ligand into a reactor, stirring for reaction under the protection of inert gas, adding a molecular sieve, heating, stirring for reaction, cooling, adding zinc powder, and stirring for reaction; 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.
Preferably, the zero-valent nickel coordination compound is one of tetrakis (trimethylphosphine) nickel, bis (1, 5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel and tetrakis (tributylphosphine) nickel.
Preferably, the coordination ligands corresponding to tetrakis (trimethylphosphine) nickel, bis (1, 5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel and tetrakis (tributylphosphine) nickel are trimethylphosphine, 1, 5-cyclooctadiene, triphenylphosphine and tributylphosphine, respectively.
Preferably, tetrahydrofuran, nickel chloride hexahydrate and a coordination ligand are added into a reactor, and the reaction is stirred at room temperature for 4-5 hours under the protection of inert gas.
Preferably, adding molecular sieve, heating to 40-80 deg.C, and stirring for 20-40 min.
In the above steps, adding molecular sieve, preferably heating to 50 deg.C, stirring and reacting for 30 min.
Preferably, zinc powder is added, and the reaction is stirred at room temperature for 1-2 h.
Preferably, methanol washing and n-hexane recrystallization are adopted.
Preferably, the inert gas is argon or nitrogen.
Has the advantages that: the invention provides a synthesis method of a zero-valent nickel coordination compound, which takes common nickel chloride hexahydrate as a nickel source, the nickel source and a coordination ligand form a divalent nickel intermediate, and the divalent nickel intermediate is efficiently reduced to form the zero-valent nickel intermediate under the action of zinc powder.
Drawings
FIG. 1 is a H1 NMR chart of tetrakis (trimethylphosphine) nickel prepared in example 1 of the present invention;
FIG. 2 is a P31 NMR chart of tetrakis (trimethylphosphine) nickel prepared in example 1 of the present invention;
FIG. 3 is a H1 NMR chart of bis (1, 5-cyclooctadiene) nickel prepared in example 2 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
0.05mol of nickel chloride hexahydrate is placed in a 250ml three-necked flask, a magnetic Teflon stirrer is added, 0.2mol of trimethylphosphine is added and 50ml of tetrahydrofuran are added. Reacting at room temperature, stirring for 4h under the protection of argon, adding 6g of dry molecular sieve, heating to 50 ℃, stirring for 30min, stirring to restore room temperature, adding 0.025mol of zinc powder, and reacting for 1 h. Under the protection of argon, a proper amount of 100 ℃ dried diatomite is added into a funnel, filtration is carried out, the solvent is removed from the filtrate in vacuum, the filtrate is washed by a proper amount of methanol, recrystallization is carried out through n-hexane, filtration and vacuum drying are carried out on the solid, and 16.5g of yellow solid, namely, nickel tetra (trimethylphosphine), is obtained, the yield is 91 percent and the purity is 99 percent.
Subjecting the obtained product to nuclear magnetic resonance hydrogen spectrum and nuclear magnetic resonance phosphorus spectrum, shown in FIGS. 1 and 2, H1 NMR (400MHz, C)6D6)：0.92(s,36H)；P31 NMR(400MHz，C6D6)：-21.5(s)。
Example 2
0.05mol of nickel chloride hexahydrate is placed in a 250ml three-necked flask, a magnetic polytetrafluoroethylene stirrer is added, 0.1mol of 1, 5-cyclooctadiene is added, and 50ml of tetrahydrofuran is added. Reacting at room temperature under the protection of argon, stirring for 4.5h, adding 6g of dry molecular sieve, heating to 40 ℃, stirring for 40min, stirring to recover to room temperature, adding 0.025mol of zinc powder, and reacting for 1.5 h. Under the protection of argon, a proper amount of 100 ℃ dried diatomite is added into a funnel, filtration is carried out, the solvent is removed from the filtrate in vacuum, the filtrate is washed by a proper amount of methanol, recrystallization is carried out through n-hexane, filtration and vacuum drying are carried out on the solid, 12.7g of bright yellow solid, namely bis (1, 5-cyclooctadiene) nickel is obtained, the yield is 92.4 percent and the purity is 99 percent.
The obtained product was subjected to nuclear magnetic resonance hydrogen spectroscopy, which is shown in FIG. 3, H1 NMR (400MHz, C)6D6)：4.30(s,8H,8CH),2.05(s,16H,8CH2)。
Example 3
0.05mol of nickel chloride hexahydrate is placed in a 250ml three-necked flask, a magnetic polytetrafluoroethylene stirrer is added, 0.2mol of triphenylphosphine is added and 50ml of tetrahydrofuran are added. Reacting at room temperature under the protection of argon, stirring for 5h, adding 6g of dry molecular sieve, heating to 80 ℃, stirring for 20min, stirring to recover the room temperature, adding 0.025mol of zinc powder, and reacting for 2 h. Under the protection of argon, a proper amount of 100 ℃ dried diatomite is added into a funnel, filtration is carried out, the solvent is removed from the filtrate in vacuum, the filtrate is washed by a proper amount of methanol, recrystallization is carried out through n-hexane, filtration and vacuum drying are carried out on the solid, 51g of yellow brown solid, namely, the nickel tetra (trimethylphosphine), is obtained, the yield is 92 percent and the purity is 99 percent.
The obtained product is made into an Elemental analysis: 78.04 for C, 5.48 for H, 5.36 for Ni and 11.12 for P.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. Economical and safe synthesis of zero-valent nickel coordination compoundThe method, the structural formula of the zero-valent nickel coordination compound is as follows: NiRnWherein the valence of Ni is zero, R is a coordination ligand, and n is the coordination number, and the synthesis method is characterized by comprising the following steps: adding tetrahydrofuran, nickel chloride hexahydrate and a coordination ligand into a reactor, stirring for reaction under the protection of inert gas, adding a molecular sieve, heating, stirring for reaction, cooling, adding zinc powder, and stirring for reaction; 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.
2. The economical and safe synthesis method of zero-valent nickel complex according to claim 1, wherein the zero-valent nickel complex is one of tetrakis (trimethylphosphine) nickel, bis (1, 5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel and tetrakis (tributylphosphine) nickel.
3. The economical and safe synthesis method of zero-valent nickel complex according to claim 2, wherein the coordinating ligands corresponding to tetrakis (trimethylphosphine) nickel, bis (1, 5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel and tetrakis (tributylphosphine) nickel are trimethylphosphine, 1, 5-cyclooctadiene, triphenylphosphine and tributylphosphine, respectively.
4. The economical and safe synthesis method of zero-valent nickel coordination compound according to claim 1, characterized in that tetrahydrofuran, nickel chloride hexahydrate and coordination ligand are added into a reactor, and the reaction is stirred at room temperature for 4-5h under the protection of inert gas.
5. The economical and safe synthesis method of the zero-valent nickel coordination compound according to claim 1, characterized in that the molecular sieve is added, the temperature is raised to 40-80 ℃, and the stirring reaction is carried out for 20-40 min.
6. The economical and safe synthesis method of zero-valent nickel complex compound according to claim 1, wherein zinc powder is added and the reaction is carried out for 1-2h under stirring at room temperature.
7. The economical and safe synthesis method of zero-valent nickel complex compound according to claim 1, characterized in that methanol washing and n-hexane recrystallization are adopted.
8. The economical and safe synthesis method of zero-valent nickel complex compound according to claim 1, wherein the inert gas is argon or nitrogen.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111972A (en) * | 1976-05-07 | 1978-09-05 | Phillips Petroleum Company | Organophosphorus nickel complexes and use thereof |
| US4120882A (en) * | 1959-12-22 | 1978-10-17 | Studiengesellschaft Kohle M.B.H. | Metal complexes |
| JP2008239584A (en) * | 2007-03-29 | 2008-10-09 | Mitsui Chemicals Inc | Production method of organic phosphine complex of zero-valent nickel |
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2020
- 2020-10-12 CN CN202011082922.3A patent/CN112159435A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120882A (en) * | 1959-12-22 | 1978-10-17 | Studiengesellschaft Kohle M.B.H. | Metal complexes |
| US4111972A (en) * | 1976-05-07 | 1978-09-05 | Phillips Petroleum Company | Organophosphorus nickel complexes and use thereof |
| JP2008239584A (en) * | 2007-03-29 | 2008-10-09 | Mitsui Chemicals Inc | Production method of organic phosphine complex of zero-valent nickel |
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