Desulfurization of organic sulfur compounds mediated by a molybdenum/cobalt/sulfur cluster

Article abstract of DOI:10.1021/ja00089a025

The bimetallic cluster Cp′₂Mo₂Co₂S₃(CO)₄ (1) reacts with organic sulfur compounds, e.g. ^tBuSH, Me₂CHCH₂CH₂SH, PhSH, ^tBuNCS, cis-2,3-dimethylthiirane, and thiophene, to give the cubane cluster Cp′₂Mo₂Co₂S₄(CO) ₂(2) in high yield. With the thiols, the organic products are the parent hydrocarbons. The thiophene desulfurization products are saturated and unsaturated C₁-C₄ hydrocarbons, and the thiocyanates produce RNC that reacts with 1 and 2 to form the carbonyl substitution products Cp′₂Mo₂Co₂S₃(CO) ₃(RNC) and Cp′₂Mo₂Co₂S₄(CO)(RNC), respectively. The cis-2,3-dimethylthiirane produces cis-2-butene stereospecifically. The mechanistic implications are discussed, and the desulfurization reactions are compared to the hydrodesulfurization (HDS) reactions catalyzed by an alumina-supported Mo/Co/S composition.