Metal-catalyzed "on-demand" production of carbonyl sulfide from carbon monoxide and elemental sulfur.

The group 6 molybdenum(II) cyclopentadienyl amidinate (CPAM) bis(carbonyl) complex [Cp*Mo{N(iPr)C(Ph)N(iPr)}(CO)2] (Cp*=η(5)-C5Me5) serves as a precatalyst for the high-yielding photocatalytic production of COS from CO and S8 under near-ambient conditions (e.g., 10 psi, 25 °C). Further documented is the isolation and structural characterization of several key transition-metal intermediates which collectively support a novel molybdenum(IV)-based catalytic cycle as being operative. Finally, in the presence of an excess amount of a primary amine, it is demonstrated that this catalytic system can be successfully used for the "on-demand" generation and utilization of COS as a chemical reagent for the synthesis of ureas.