Herberhold, MaxHill, Anthony F.2026-01-042026-01-040022-328XORCID:/0000-0003-2167-0604/work/171153973https://hdl.handle.net/1885/733803510Neutral hydrido complexes [ML]ClH(PPh3)3 ([ML] = Ru(CO), Os(CO) and Ir(Cl)] react with thionitrosodimethylamine, Me2NNS, to give [ML]ClH-(SNNMe2)(PPh3)2 with H trans to Me2NNS, while the hydrido cations cis,trans-[[ML]H(SNNMe2)2(PPh3)2]+ are obtained from Me2NNS and [Ru(NCMe)2(CO)-(PPh3)2]+, [OsH(OH2)(CO)(PPh3)3]+ and [IrClH(NCMe)2(PPh3)2]+, respectively. The coordinatively unsaturated aryl complexes [ML′]Cl(p-tolyl)(PPh3)2 ([ML′]Ru(CO), Os(CO) and Os(CS)) coordinate one molecule of Me2NNS to give [ML′]Cl(p-tolyl)(SNNMe2)(PPh3)2, the chloride ligands of which are labile. Spectroscopic data suggest that in all these complexes the Me2NNS ligand adopts a η1(S) coordination mode.We gratefully acknowledge the financial support of the Deutsche Forschungs-gemeinschaft and the Fonds der Chemischen Industrie. We also thank the Deutsche Akademische Austauschdienst for a fellowship (to A.F.H.). Iridium salts were generously loaned by Johnson-Matthey Ltd.8en1986-11-0410.1016/0022-328X(86)80415-60542443858