Late transition metal complexes derived from diphosphazane monosulfide ligands: X-ray crystal structures of [Ru3(μ-CO)(CO)7(μ3-S){Ph2PN((S)-*CHMePh)PPh2-κ2P,P}] and [Rh(CO)Cl{Ph2PN((S)-*CHMePh)P(S)Ph2}-κ2P,S]: Part 16. Organometallic chemistry of diphosph

The oxidative addition reactions of diphosphazane monosulfides, Ph2PN(R)P(S)Ph2 (R=(S)-*CHMePh (1), CHMe2 (2)) with [Ru3(CO)12] afford sulfur-monocapped triruthenium clusters of the type [Ru3(μ-CO)(CO)7(μ3-S){Ph2PN(R)PPh2-κ2P,P}] (R=(S)-*CHMePh (3), CHMe2 (4)); the X-ray crystal structure of 3 reveals the chelating mode of coordination of the diphosphazane ligand, which is rarely observed for such type of complexes. The bridge-splitting reactions of 1 and 2 with [{Rh(μ-Cl)(CO)2}2] yield [Rh(CO)Cl{Ph2PN(R)P(S)Ph2-κ2P,S}] (R=(S)-*CHMePh (5), CHMe2 (6)); the X-ray crystal structure of 5 confirms that the ‘CO’ ligand is trans to the PS bond. The reactions of [MCl2(COD)] with 1 and 2 yield chelate complexes, [MCl2{Ph2PN(R)P(S)Ph2-κ2P,S}] [M=Pd (7 and 8) or Pt (9 and 10)].