Synthesis and diastereoselective ligand substitution reaction of a mono(sulfido)-bridged Ir-Mo heterodinuclear complex

Mono(sulfido)-bridged heterodinuclear complexes [Cp∗IrH(PPh3)(μ-S)MCl(NO)Cp∗] (M = Mo, W) are obtained by the reaction of the hydrido-hydrosulfido complex [Cp∗IrH(SH)(PPh3)] with [Cp∗MCl2(NO)]. Treatment of the Ir-Mo complex with [Ph3C][BF4] in CH2Cl2-MeCN gives the acetonitrile complex [Cp∗Ir(NCMe)(PPh3)(μ-S)MoCl(NO)Cp∗][BF4] with high diastereoselectivity, where the stereochemical course of the reaction has been revealed by X-ray analysis.