New heterometallic cubane-like clusters [{(eta(5)-Cp)Mo}(3)S-4{M '(CO)(3)}](pts) (M ' = Cr, Mo, W; pts = p-toluenesulfonate) obtained by ligand substitution reactions and insertion of {M '(CO)(3)} fragments

A series of group 6 heterometallic sulfide clusters have been prepared to e stablish a route to potential models of hydrodesulfurization catalysts suit able for application in nonaqueous media. The cluster compound [{(H2O)(3)Mo }(3)S-4](Pts)(4). 9H(2)O (pts = p-toluenesulfonate) was treated with trieth yl orthoformate in the presence of a catalytic amount of Hpts to yield an e thanol complex of the [Mo3S4](4+) cluster core. The complex was subsequentl y converted in situ to acetonitrile and tetrahydrofuran complexes before tr eatment with thallium cyclopentadienide to yield the new cluster compound [ {(eta(5)-Cp)Mo}(3)S-4](pts) (1). Insertion of {M'(CO)(3)} fragments into 1 afforded the series of cubane-like, heterometallic clusters [({eta(5)-Cp)Mo }(3)S-4{M'(CO)(3)}](pts) (M' = Cr (2a), Mo (2b), W (2c)). Single-crystal X- ray analysis established the heterometallic S-4-capped tetrahedral cluster core in the structure of 2c.1/2-CH3OH.