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(ButNSPh), gave two products, Ru(η4-C5Me4CH2)(η2-ButNSPh)Cl 1 and the dimer Cl(η-C5Me5)Ru(µ-NBut)(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 CrV(η-C5Me5)(NBut)(SPh)23, in the interaction of Li(ButNSPh) 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(ButNSPh) gave Ni(η2-ButNSPh)2(PMe3)5. The structures of compounds 1–5 have been confirmed by X-ray crystallography.