The ruthenacyclic carbamoyl complexes [RuX{2-NHC(O)C5H3NR}(CO)2(NCMe)] (R = H and Me; X = Br and SC6H3-o,o-Me2) are excellent catalysts for the hydrolysis of organosilanes, particularly towards primary silanes, generating hydrogen under ambient conditions within seconds. These complexes are structural mimics of the [Fe]-hydrogenase active site and like the natural enzyme, a labile ligand at the sixth coordination site is essential to the catalytic activity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim