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.