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

Single-crystal X-ray crystallography is employed to characterize the reaction species of a full catalytic carbonylation cycle within a Mn-II-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 Me-I. This work highlights the capability of MOFs to act as platform materials for studying single-site catalysis in heterogeneous systems.