An unsaturated half-sandwich ruthenium(II) complex containing a dithioimidodiphosphinate ligand

Treatment of [Cp*RuCl2]x (Cp* = η5-C5Me5) with K[N(Ph2PS)2] afforded [Cp*Ru{N(Ph2PS)2}Cl] (1). Reduction of 1 with Li[BEt3H] gave the 16-electron half-sandwich Ru(II) complex [Cp*Ru{N(Ph2PS)2}] (2). Complexes 1 and 2 have been characterized by X-ray crystallography. The Ru–Cp*(centroid) and average Ru–S distances in 1 are 1.827 and 2.3833(5) Å, respectively. The corresponding bond distances in 2 are 1.739 and 2.379(1) Å. Treatment of 2 with 2-electron ligands L afforded the adducts [Cp*Ru{N(Ph2PS)2}L] (L = CO (3), 2,6-Me2C6H4NC (4), MeCO2CCCO2Me (5)). Oxidation of 2 with tetramethylthiuram disulfide gave the Ru(IV) complex [Cp*Ru{S2CNMe2}2][N(Ph2PS)2] (6). The Ru–Cp*(centroid) and average Ru–S distances in 6 are 1.897 and 2.387(1) Å, respectively.

Graphical abstractReduction of [Cp*Ru{N(Ph2PS)2}Cl] (Cp* = η5-C5Me5) with Li[BEt3H] gives the 16-electron unsaturated Ru(II) complex [Cp*Ru{N(Ph2PS)2}], which exhibits an approximately perpendicular arrangement between the Cp* ring and the Ru-S-S′ plane. [Cp*Ru{N(Ph2Ps)2}] reacts with 2-electron ligands L to give the 18-electron adducts [Cp*Ru{N(Ph2PS)2}(L)] (L = CO, isocyanide and alkyne).Figure optionsDownload full-size imageDownload as PowerPoint slide