Angewandte Chemie - International Edition
Angewandte Chemie - International Edition
5 years ago

Mapping-Out Catalytic Processes in a Metal–Organic Framework with Single-Crystal X-ray Crystallography

Mapping-Out Catalytic Processes in a Metal–Organic Framework with Single-Crystal X-ray Crystallography
Gregory F. Metha, Campbell J. Coghlan, Satoshi Horike, Wenqian Chen, David M. Huang, Alexandre Burgun, Christopher J. Sumby, Jason F. Alvino, Susumu Kitagawa, Christian J. Doonan
Single-crystal X-ray crystallography is employed to characterize the reaction species of a full catalytic carbonylation cycle within a MnII-based metal–organic framework (MOF) material. The structural insights explain why the Rh metalated MOF is catalytically competent toward the carbonylation of MeBr but only affords stoichiometric turn-over in the case of MeI. This work highlights the capability of MOFs to act as platform materials for studying single-site catalysis in heterogeneous systems. Crystallization not needed: A MnII-based MOF is used as a matrix to isolate and structurally elucidate the chemistry of a single-site rhodium(I) catalyst that carries out the carbonylation of methyl halides. X-ray crystal structures of catalytic intermediates were obtained and explain why carbonylation occurs with MeBr but not MeI.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201611254

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