The synthesis of thionitrosodimethylamine (Me₂NNS) complexes of ruthenium, osmium, and iridium

Abstract

Neutral 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.