Abstract

A series of group 6 heterometallic sulfide clusters have been prepared to establish a route to potential models of hydrodesulfurization catalysts suitable for application in nonaqueous media. The cluster compound [{(H2O)3Mo}3S4](pts)4·9H2O (pts = p-toluenesulfonate) was treated with triethyl orthoformate in the presence of a catalytic amount of Hpts to yield an ethanol complex of the [Mo3S4]4+ cluster core. The complex was subsequently converted in situ to acetonitrile and tetrahydrofuran complexes before treatment with thallium cyclopentadienide to yield the new cluster compound [{(η5-Cp)Mo}3S4](pts) (1). Insertion of {M‘(CO)3} fragments into 1 afforded the series of cubane-like, heterometallic clusters [{(η5-Cp)Mo}3S4{M‘(CO)3}](pts) (M‘ = Cr (2a), Mo (2b), W (2c)). Single-crystal X-ray analysis established the heterometallic S4-capped tetrahedral cluster core in the structure of 2c·1/2CH3OH.