Allenylidene and diazoalkane complexes of a half-sandwich mixed phosphine - phosphinite ruthenium fragment

Abstract Half-sandwich mixed phosphine-phosphinite ruthenium complexes [RuCp’Cl(PPh3)L] [Cp’ = Cp (1), Cp* (2)], and [RuCp*ClL2] (3) were prepared by substitution of the triphenylphosphine by the phosphinite ligand PPh2OCH2Ph, L, on the parent complexes [RuCp’Cl(PPh3)2]. Allenylidene compounds [Ru(η5-C5H5){ C C = CPh2}(PPh3)L][PF6] (4) and [Ru(η5-C5Me5){ C C = CPhR}(L)(L’)][BPh4] [L’ = PPh3 (5), L (6); R = Ph (a), R = Me (b)] were obtained by reaction of compounds 1–3 with the appropriate propargylic alcohols 1,1-diphenyl-2-propyn-1-ol, and 2-phenyl-3-butyn-2-ol. Diazoalkane complexes [RuCp(N2CAr1Ar2)(PPh3)L][PF6] [Ar1 = Ar2 = Ph (7a), Ar1Ar2 = C12H8 (7b)] and [RuCp*{N2C(C12H8)}L2][PF6] (8) were obtained by reaction of 1 or 3 with the corresponding diazoalkanes in the presence of NaPF6. Complexes were characterized by IR and NMR spectroscopy and, in the case of compounds 1 and 7a, by X-ray diffraction analysis.