New Heterometallic Cubane-Like Clusters [{(η5-Cp)Mo}3S4M'(CO)3](pts) (M' = Cr, Mo, W; pts = p-Toluenesulfonate) Obtained by Ligand Substitution Reactions and Insertion of {M'(CO)3 Fragments

Article abstract of DOI:10.1021/om990029f

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)Mo}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 [{(η⁵5-Cp)Mo}₃S₄](pts) (1). Insertion of {M'-(C0)₃ fragments into 1 afforded the series of cubane-like, heterometallic clusters [{(η⁵- Cp)Mo}₃S₄M'(CO)₃](pts) (M' = Cr (2a), Mo (2b), W (2c)). Single-crystal X-ray analysis established the heterometallic S₄capped tetrahedral cluster core in the structure of 2c.1/2- CH₃OH.