Molecular and Crystal Structures of CpM(S2N2) (M = Co, Rh, Ir) and Related Compounds

Cp*Rh(S2N2) was prepared as a microcrystalline solid by using [S4N3]Cl in liquid ammonia or [nBu2Sn(S2N2)]2. It was characterised by NMR, IR and Raman spectroscopy andmass spectrometry. Low‐temperature crystal structures of Cp*Co(S2N2) and Cp*Ir(S2N2) were determined. The experimental characterisation of the Cp*M(S2N2) complexes was complemented by calculated geometries and bond orders at the DFT/B1B95 level of theory. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) Metallasulfur–nitrogen chemistry continues to surprise theoreticians and synthetic chemists. During the synthesis of a simple MS2N2 complex we obtained a binuclear complex.