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 [Cp

The reaction of [CpMo(CO)3]2 (1) with a molar equivalent of Bz2S3 at 60 °C for 3.5 h has led to the isolation of [CpMo(CO)2(SBz)]2 (2), [CpMo(CO)(SBz)]2S (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 μ–η2-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.

Graphical abstractThe reactivity study of [CpMo(CO)3]2 (1) with a molar equivalent of Bz2S3 at 60 °C has led to the isolation of the primary product of [CpMo(CO)2(SBz)]2 (2) which underwent decarbonylation and sulfur insertion to give secondary product of [CpMo(CO)(SBz)]2S (3). Thermolytic studies showed the degradation of 2 and 3 finally gave [CpMo(SBz)S]2 (4) as the ultimate thermolytic product.Figure optionsDownload full-size imageDownload as PowerPoint slide