Solid-supported binuclear rhodium metal complex catalyst and its preparation method and application

A metal complex and catalyst technology, applied in the field of immobilized dual-nuclear rhodium metal complex catalyst and its preparation, can solve problems such as no reports, and achieve the effects of simple and fast method, large specific surface area and stable structure

Inactive Publication Date: 2020-07-28
SHANGHAI NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Therefore, ZIF-8 is currently widely used as a carrier to immobilize noble metal nanoparticles, metal oxides, and bioactive drugs, but there is no report on its application as a carrier to immobilize metal complexes.

Method used

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  • Solid-supported binuclear rhodium metal complex catalyst and its preparation method and application
  • Solid-supported binuclear rhodium metal complex catalyst and its preparation method and application
  • Solid-supported binuclear rhodium metal complex catalyst and its preparation method and application

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preparation example Construction

[0024] The embodiment of the present invention also provides a preparation method of a solid-supported binuclear rhodium metal complex catalyst, comprising: making the 2 (esp) 2 The mixed system of 2-methylimidazole and solvent reacts at room temperature to form 2-methylimidazole axially modified Rh 2 (esp) 2 , and then add Zn to the mixed system 2+ , react at room temperature to obtain a solid-supported binuclear rhodium metal complex catalyst.

[0025] In some more specific embodiments, the preparation method comprises: at room temperature, to Rh 2 (esp) 2 2-Methylimidazole was added to the methanol solution to react until the color of the solution changed from green to light red, and Rh containing 2-Methylimidazole axial modification was obtained. 2 (esp) 2 The reaction mixture, and then add soluble zinc salt to the reaction mixture for reaction to obtain a solid-supported binuclear rhodium metal complex catalyst.

[0026] Further, wherein the amount of 2-methylimida...

Embodiment 1

[0039] Example 1: Immobilized Rh in one-step method 2 (esp) 2 Preparation of:

[0040] Step 1: 2-Methylimidazole and Rh 2 (esp) 2 Axial coordination: the Rh 2 (esp) 2 Dissolve in 10mL methanol solution respectively to obtain a clear green solution with a concentration below 3.0mg / mL, then add 4.0mmol of 2-methylimidazole, and wait until the solution changes from green to light red, at this time, the solution containing axial Ligand 2-methylimidazole modified Rh 2 (esp) 2 A reaction mixture in which the axial ligand 2-methylimidazole-modified Rh 2 (esp) 2 The X-ray photoelectron spectrum of figure 2 shown.

[0041] Step 2: Self-assembly to form ZIF-8: Slowly add zinc nitrate aqueous solution dropwise to the aforementioned reaction mixture at room temperature, and magnetically stir for 2 hours to allow self-assembly to prepare Rh 2 (esp) 2 complex with ZIF-8. Then centrifuged and washed with methanol solution to obtain the immobilized Rh 2 (esp) 2 Composite mater...

Embodiment 2

[0043] Embodiment 2: the Rh 2 (esp) 2 The process of using @ZIF-8 to catalyze the synthesis of N-H propane ring compounds is as follows:

[0044] The reaction was carried out in a 10mL reaction flask, and 0.55mmol of 2,4-dinitrophenylhydroxylamine, 0.005mmolRh 2 (esp) 2 The @ZIF-8 catalyst was added to the reaction bottle, and then filled with nitrogen gas after vacuuming with an oil pump. This was done three times, and then 5.0 mL of 2,2,2-trifluoroethanol solvent and 0.50 mmol of 2- Methyl-1-phenylpropene was reacted for 3h at room temperature. Take 0.60 μL of the clear liquid of the reaction product, and quantitatively analyze the reaction product with a gas chromatograph, and the results are shown in Table 1:

[0045] Table 1 is the result of quantitative analysis of the reaction product by gas chromatography

[0046] catalyst Reaction time (h) Conversion rates(%) selectivity (%) Yield(%) 1mol% Rh 2 (esp) 2 @ZIF-8

3 96 82 79

[00...

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Abstract

The invention discloses a preparation method and application of an immobilized binuclear rhodium metal complex catalyst. The immobilized binuclear rhodium metal complex catalyst is prepared from a metallic organic framework ZIF-8 which is formed by Zn<2+> and 2-methylimidazole and serves as a carrier as well as Rh[2](esp)[2] which is axially modified by the 2-methylimidazole and is distributed onthe carrier ZIF-8. The preparation method comprises the following steps: enabling a mixed system containing the Rh[2](esp)[2], the 2-methylimidazole and a solvent to be subjected to reaction under theroom temperature condition to form the Rh[2](esp)[2] axially modified by the 2-methylimidazole, and then, adding the Zn<2+> into the mixed system to be subjected to reaction at room temperature to obtain the immobilized binuclear rhodium metal complex catalyst. The 2-methylimidazole is adopted as an organic ligand for synthesizing the ZIF-8, is self-assembled with zinc ions to form the metallic framework of the ZIF-8, and is in axial coordination with the Rh[2](esp)[2]; and after coordination, not only the reaction activity of the Rh[2](esp)[2] is not affected, but the reaction selectively for catalytic synthesis of N-H propane compounds is improved, and the universality is realized.

Description

technical field [0001] The invention particularly relates to a solid-supported dinuclear rhodium metal complex catalyst and its preparation method and application, belonging to the technical field of material synthesis. Background technique [0002] Rh 2 (esp) 2 As a unique homonuclear bimetallic compound, there is a rhodium-rhodium bond between the metal cores, and it often exhibits a different reaction mode from mononuclear metal compounds when catalyzing organic reactions. Rh 2 (esp) 2 It has high catalytic activity for catalyzing the synthesis of carbene and nitrene species, however Rh 2 (esp) 2 The price is very expensive, and it has been used in a homogeneous system in the catalytic reaction, so it cannot be reused, which will easily cause the loss of precious metals and environmental pollution. Metal-organic framework ZIF-8 is a rhombic dodecahedral structure with a particle size distribution of 50-80nm and uniform pore size, and has a large specific surface are...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/22B01J32/00C07D203/14
CPCB01J31/1658B01J31/1691B01J31/1815B01J31/2213B01J2231/74B01J2531/0219B01J2531/0241B01J2531/26B01J2531/822C07D203/14
Inventor 张昉李震忠刘金秀李树媛李松曹林清
Owner SHANGHAI NORMAL UNIVERSITY
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