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 diphosphazanes

Abstract

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)].