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In Situ Generation of an N‐Heterocyclic Carbene Functionalized Metal–Organic Framework by Postsynthetic Ligand Exchange: Efficient and Selective Hydrosilylation of CO 2
Author(s) -
Zhang Xu,
Sun Jiao,
Wei Guangfeng,
Liu Zhipan,
Yang Huimin,
Wang Kaimin,
Fei Honghan
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201813064
Subject(s) - chemistry , hydrosilylation , carbene , catalysis , metal organic framework , ligand (biochemistry) , silanes , silylation , combinatorial chemistry , heterogeneous catalysis , silane , polymer chemistry , organic chemistry , adsorption , biochemistry , receptor
The reported metal–organic framework (MOF) catalyst realizes CO 2 to methanol transformation under ambient conditions. The MOF is one rare example containing metal‐free N‐heterocyclic carbene (NHC) moieties, which are installed using an in situ generation strategy involving the incorporation of an imidazolium bromide based linker into the MOF by postsynthetic ligand exchange. Importantly, the resultant NHC‐functionalized MOF is the first catalyst capable of performing quantitative hydrogen transfer from silanes to CO 2 , thus achieving quantitative (>99 %) methanol yield. Density‐functional theory calculations indicate the high catalytic activity of the NHC sites in MOFs are attributed to the decreased reaction barrier of a reaction route involving the formation of an NHC‐silane adduct. In addition, the MOF‐immobilized NHC catalyst shows enhanced stability for up to eight cycles without base activation, as well as high selectivity towards the desired silyl methoxide product.