Synthesis and crystal structures of η2-sulfenamido complexes of ruthenium and nickel, and of chromium imido and cobalt iminophosphorane complexes via sulfenamido rearrangement

Abstract

The interaction of [Ru(η-C₅Me₅)Cl₂]₂ with Li(Bu^tNSPh), gave two products, Ru(η⁴-C₅Me₄CH₂)(η²-Bu^tNSPh)Cl 1 and the dimer Cl(η-C₅Me₅)Ru(µ-NBu^t)(µ-SPh)Ru(η-C₅Me₅)2; the former is best described as a η⁴-tetramethylfulvene ruthenium(II) complex, while in the latter the bridging tert-butylimido and benzene-thiolato groups were formed by S–N cleavage of sulfenamido species. A similar cleavage resulted in the formation of Cr^V(η-C₅Me₅)(NBu^t)(SPh)₂3, in the interaction of Li(Bu^tNSPh) with [Cr(η-C₅Me₅)Br₂]₂. Interaction of CoCl₂(PMe₃)₃ with Li(p-MeC₆H₄NSPh) gave the iminophosphorane complex Co(p-MeC₆H₄NPMe₃)₂(SPh)₂4. Interaction of NiCl₂(PMe₃)₂ with Li(Bu^tNSPh) gave Ni(η²-Bu^tNSPh)₂(PMe₃)5. The structures of compounds 1–5 have been confirmed by X-ray crystallography.