Novel ruthenium(II) complexes containing the N-phosphorylated iminophosphorane-phosphine ligand Ph2PCH2P{=NP(=O)(OEt)2}Ph2: a new coordination mode of its methanide anion

The reactivity of complex [Ru(eta(6)-p-cymene)(k(3)P, N, O-Ph2PCH2P{=NP(=O)(OEt)(2)} Ph-2)][SbF6] (2) 1 towards a variety of mono- and bidentate neutral ligands has been studied, allowing the high-yield synthesis of the novel half-sandwich Ru(II) derivatives [Ru(eta(6)-p-cymene)(L)(k(2)P, O-Ph2PCH2P{=NP(=O)(OEt)(2)}Ph-2)][SbF6](2) (L = N CMe 3a, N CEt 3b, PMe3 4a, PMe2Ph 4b, PMePh2 4c, PPh3 4d, P(OMe)(3) 5a, P(OEt)(3) 5b, P(OPh)(3) 5c, py 6, k(1)P-dppm 7a, k(1)P-dppe 7b), as well as the octahedral species [Ru((NN)-N-boolean AND)(2)(k(2)P, O-Ph2PCH2P{=NP(=O)(OEt)(2)}Ph-2)][SbF6](2) ((NN)-N-boolean AND = bipy 8a, phen 8b). Deprotonation of complexes 8a, b, upon treatment with an excess of NaOH in CH2Cl2, generates the monocationic derivatives [Ru((NN)-N-boolean AND)(2)(k(2)P, N-Ph2PC(H)=P{NP(=O)(OEt)(2)}Ph-2)][Cl] ((NN)-N-boolean AND = bipy 9a, phen 9b) in which the methanide anion adopts an unprecedented k(2)P, N bidentate coordination mode. The structures of compounds 6, 8a and 9a have been determined by single-crystal X-ray diffraction methods.