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与金属杂环卡宾键合的金属有机框架用于高效催化。

Metal-organic frameworks bonded with metal -heterocyclic carbenes for efficient catalysis.

作者信息

He Chang, Liang Jun, Zou Yu-Huang, Yi Jun-Dong, Huang Yuan-Biao, Cao Rong

机构信息

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China.

出版信息

Natl Sci Rev. 2021 Aug 24;9(6):nwab157. doi: 10.1093/nsr/nwab157. eCollection 2022 Jun.


DOI:10.1093/nsr/nwab157
PMID:35822067
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9270066/
Abstract

Metal heterocyclic carbenes (M-NHCs) on the pore walls of a porous metal-organic framework (MOF) can be used as active sites for efficient organic catalysis. Traditional approaches that need strong alkaline reagents or insoluble AgO are not, however, suitable for the incorporation of NHCs on the backbones of MOFs because such reagents could destroy their frameworks or result in low reactivity. Accordingly, development of facile strategies toward functional MOFs with covalently bound M-NHCs for catalysis is needed. Herein, we describe the development of a general and facile approach to preparing MOFs with covalently linked active M-NHC (M = Pd, Ir) single-site catalysts by using a soluble Ag salt AgOC(CF) as the source and subsequent transmetalation. The well-defined M-NHC-MOF (M = Pd, Ir) catalysts obtained in this way have shown excellent catalytic activity and stability in Suzuki reactions and hydrogen transfer reactions. This provides a general and facile strategy for anchoring functional M-NHC single-site catalysts onto functionalized MOFs for different reactions.

摘要

多孔金属有机框架(MOF)孔壁上的金属杂环卡宾(M-NHC)可作为高效有机催化的活性位点。然而,传统方法需要强碱性试剂或不溶性的AgO,不适用于将NHC引入MOF骨架,因为这些试剂可能会破坏其框架或导致低反应活性。因此,需要开发简便的策略来制备具有共价连接的M-NHC用于催化的功能化MOF。在此,我们描述了一种通用且简便的方法,通过使用可溶性Ag盐AgOC(CF)作为来源并随后进行金属转移反应,制备具有共价连接的活性M-NHC(M = Pd、Ir)单位点催化剂的MOF。以这种方式获得的定义明确的M-NHC-MOF(M = Pd、Ir)催化剂在铃木反应和氢转移反应中表现出优异的催化活性和稳定性。这为将功能性M-NHC单位点催化剂锚定到功能化MOF上以进行不同反应提供了一种通用且简便的策略。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7af1/9270066/9db3317a5134/nwab157fig5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7af1/9270066/1ed9b728988b/nwab157sc1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7af1/9270066/45872c49382b/nwab157fig1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7af1/9270066/0e4889c999e2/nwab157fig2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7af1/9270066/41ccd6450b0d/nwab157fig3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7af1/9270066/1700b3803850/nwab157fig4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7af1/9270066/9db3317a5134/nwab157fig5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7af1/9270066/1ed9b728988b/nwab157sc1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7af1/9270066/45872c49382b/nwab157fig1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7af1/9270066/0e4889c999e2/nwab157fig2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7af1/9270066/41ccd6450b0d/nwab157fig3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7af1/9270066/1700b3803850/nwab157fig4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7af1/9270066/9db3317a5134/nwab157fig5.jpg

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本文引用的文献

[1]
Encapsulating metal organic framework into hollow mesoporous carbon sphere as efficient oxygen bifunctional electrocatalyst.

Natl Sci Rev. 2020-3

[2]
Multielectron transportation of polyoxometalate-grafted metalloporphyrin coordination frameworks for selective CO-to-CH photoconversion.

Natl Sci Rev. 2020-1

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Natl Sci Rev. 2020-1

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Natl Sci Rev. 2020-5-8

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Natl Sci Rev. 2019-11-5

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Natl Sci Rev. 2020-7-15

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Angew Chem Int Ed Engl. 2021-9-13

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Docking of Cu and Ag in Metal-Organic Frameworks for Adsorption and Separation of Xenon.

Angew Chem Int Ed Engl. 2021-2-15

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Modulating Single-Atom Palladium Sites with Copper for Enhanced Ambient Ammonia Electrosynthesis.

Angew Chem Int Ed Engl. 2021-1-4

[10]
Filling metal-organic framework mesopores with TiO for CO photoreduction.

Nature. 2020-10

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