CYCLOPENTADIENYL-RUTHENIUM AND CYCLOPENTADIENYL-OSMIUM CHEMISTRY .7. COMPLEXES CONTAINING NITRILES, TERTIARY PHOSPHINES OR PHOSPHITES FORMED BY ADDITION OR DISPLACEMENT-REACTIONS

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-CsH5)]+ (R = CH2C1, CH2=CH, CH2=CC1, Ph, C6Fs, CH2CN, CH2C02Et, 2-NCC6H4, 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 RuCl(PPh3)2(η-C5H5) or OsBr(PPh3)2(η-C5H5) by tertiary phosphines or phosphites has given the complexes RuC1(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)] + (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-C5Hs)]- [L = P(OMe)3; L3 = MeC(CH2PPh2)3 or EtC(CH2PPh2)3] and [Os(NCMe)(PPh3)2- (η-C5H5)] +are also described. © 1979 ASEG.