OXIDATIVE SUBSTITUTION OF CARBONYL GROUPS BY HALOGEN OR RS-CENTER-DOTON THE CUBANE CLUSTER (CP2MO2CO2S4)-MO-ET(CO)(2) - PREPARATION OF 58-VSE ELECTRON-DEFICIENT CLUSTERS AS MODELS FOR AN ORGANOMETALLIC DESULFURIZATION MATERIAL

The heterobimetallic sulfide cluster (Cp2Mo2Co2S4)-Mo-Et(CO)(2) was ox idized to give a series of 58-VSE (valence shell electron) electron-de ficient clusters of the type (Cp2Mo2Co2S4)-Mo-Et(X)(2)(X = I, Br, Cl, SPh). These clusters have been structurally characterized by X-ray dif fraction. Their magnetic behavior was investigated to reveal complex s pin equilibria for the halide-substituted clusters (X = I, Br, Cl) and simple paramagnetism for the thiolate substituted cluster (X = SPh). In an attempted catalytic reaction, (Cp2Mo2Co2S4)-Mo-Et(CO)(2) reacted with excess benzene thiol under 1000 psi of CO at 150 degrees C to gi ve phenylthiobenzoate, PhS(CO)-Ph, and PhSSPh in excess of the stoichi ometric amounts.