American Chemical Society
om990029f_si_001.cif (24.74 kB)

New Heterometallic Cubane-Like Clusters [{(η5-Cp)Mo}3S4{M‘(CO)3}](pts) (M‘ = Cr, Mo, W; pts = p-Toluenesulfonate) Obtained by Ligand Substitution Reactions and Insertion of {M‘(CO)3} Fragments

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posted on 1999-05-20, 00:00 authored by Barbara Rink, Michael Brorson, Ian J. Scowen
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.