A novel application of a transition metal oxo complex, a cationic oxorhenium(V) oxazoline, in the production of molecular hydrogen (H2) from the catalytic hydrolytic oxidation of organosilanes. The reaction is characterized by quantitative hydrogen yields, low catalyst loading, ambient conditions, high selectivity for silanols, water as the only co-reagent, and no solvent requirement. The amount of hydrogen produced is proportional to the water stoichiometry. For example, reaction mixtures of polysilyl organics such as HC(SiH3)3 and water contain potentially greater than 6 weight percent hydrogen. Kinetic and isotope labeling experiments reveal a new mechanistic paradigm for the activation of Si—H bonds by oxometalates.