Cyclopentadienyl-ruthenium and -osmium Chemistry. VII. Complexes Containing Nitriles, Tertiary Phosphines or Phosphites Formed by Addition or Displacement Reactions

Abstract

Cationic complexes were obtained from RuCl(PPh₃)₂(η-C₅H₅) and a variety of nitriles, tertiary phosphines and phosphites. Nitriles afforded the cations [Ru(NCR)(PPh₃)₂(η-C₅H₅)]⁺ (R = CH₂Cl, CH₂ = CH₂ CH₂ = CCl, Ph, C₆F₅, CH₂CN, CH₂CO₂Et, 2-NCC,₆H₄, 2-NCC₆F₄ or 4-NH₂C₆H₄) and {R[(CN)Ru(PPh₃)₂(η-C₅H₅)]₂}²⁺ (R = 1,2-C₂H₄, 1,3-C₆H₄ or 1,4-C₆F₄). Displacement of PPh₃ from RUCI(PPh₃)₂(η-C₅H₅) or OsBr(PPh₃)₂(η-C₅H₅) by tertiary phosphines or phosphites has given the complexes Rul(L₂)(η-C₅H₅) [L = P(OMe)₃; L₂ = dppm, dppe], OsBr(L)(PPh₃)(η-C₅H₅) [L = P(OMe)₃, P(OPh)₃] and OsBr(L₂)(η-C₅H₅) [L = P(OMe)₃, P(OPh)₃; L₂ = dppm]. The cationic complexes {Ru(PPh₃)₂[P(OMe)₃](η-C₅H₅)}⁺, [Ru(L₂)(PPh₃)(η-C₅H₅)l⁺ (L₂ = dppm or dppe), {[M(PPh₃)₂(η-C₅H₅)]₂(L₂)}²⁺ [M = Ru, L₂ = C₂(PPh₂)₂; M = Os, L₂ = dppe], [Ru(L₃)- (η-C₅H₅)]⁺ [L = P(OMe)₃; L₃ = MeC(CH₂PPh₂)₃ or EtC(CH₂PPh₂)₃] and [OS(NCMe)(PPh₃)₂ (η-C₅H₅)]⁺ are also described.