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

Abstract

The reactivity of complex [Ru(η⁶-p-cymene)(κ³P,N,O-Ph₂PCH₂P{NP(O)(OEt)₂}Ph₂)][SbF₆]₂1 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(η⁶-p-cymene)(L)(κ²P,O-Ph₂PCH₂P{NP(O)(OEt)₂}Ph₂)][SbF₆]₂ (L = NCMe 3a, NCEt 3b, PMe₃4a, PMe₂Ph 4b, PMePh₂4c, PPh₃4d, P(OMe)₃5a, P(OEt)₃5b, P(OPh)₃5c, py 6, κ¹P-dppm 7a, κ¹P-dppe 7b), as well as the octahedral species [Ru(N⁁N)₂(κ²P,O-Ph₂PCH₂P{NP(O)(OEt)₂}Ph₂)][SbF₆]₂ (N⁁N = bipy 8a, phen 8b). Deprotonation of complexes 8a,b, upon treatment with an excess of NaOH in CH₂Cl₂, generates the monocationic derivatives [Ru(N⁁N)₂(κ²P,N-Ph₂PC(H)P{NP(O)(OEt)₂}Ph₂)][Cl] (N⁁N = bipy 9a, phen 9b) in which the methanide anion adopts an unprecedented κ²P,N bidentate coordination mode. The structures of compounds 6, 8a and 9a have been determined by single-crystal X-ray diffraction methods.