UiO-type metal-organic frameworks with NHC or metal-NHC functionalities for N-methylation using CO2 as the carbon source.

We demonstrate the first metal-organic framework (MOF) that catalyzes N-methylation of amines using 1 atm CO2 and phenylsilane under ambient conditions. Compared with its homogeneous analog, the incorporation of N-heterocyclic carbene (NHC) into the MOF provides more efficient catalysis with improved reaction kinetics, turnover numbers and recyclability. Moreover, the metalated NHC functionalized MOF achieves direct N-methylation of amines bearing carboxylate moieties, which are common building blocks in pharmaceutical chemistry.