Desulfurization of bibenzyl trisulfide by [CpMo(CO)3]2:: Formation and isolation of thiolato-bridged dimolybdenum complexes of [CpMo(CO)2(SBz)]2, [CpMo(CO)(SBz)]2S and [CpMo(SBz)S]2 (Cp = (η5-C5H5), Bz = PhCH2-).: Crystal structures of two polymorphs of [CpMo(SBz)S]2

The reaction of [CpMo(CO)(3)](2) (1) with a molar equivalent of Bz(2)S(3) at 60 degrees C for 3.5 h has led to the isolation of [CpMo(CO)(2)(SBz)](2) (2), [CpMo(CO)(SBz)](2)S (3) and [CpMo(SBz)S](2) (4) in 16.9%, 3.1% and 61.1% yields, respectively, as main products. Thermolytic studies showed that 2 underwent stepwise decarbonylation to give 3 and 4. All the three products of 2, 3 and 4 were thiolato-bridged dimolybdenum complexes with bond orders of zero, one and two for 2, 3 and 4, respectively. In addition, both 3 and 4 have one and two S atoms bridged in a mu-eta(2)-mode, respectively. The structures of 2 and 3 have been reported previously. The totally decarbonylated 4 was isolated as polymorphs, 4a and 4b, which have been characterized by elemental, spectral analyses and structurally determined. (c) 2007 Elsevier B.V. All rights reserved.