Novel (η6-arene)-ruthenium(II) complexes containing bis(iminophosphorano)methanide and methandiide ligands

The novel bis(iminophosphorano)methanes CH2[P{double bond; length as m-dashNP(double bond; length as m-dashS)(OR)2}Ph2]2 (R = Ph (1a), Et (1b)) have been obtained by oxydation of dppm with the corresponding thiophosphorylated azides (RO)2P(double bond; length as m-dashS)N3. Deprotonation of 1a,b with KH generates the methanide species KCH[P{double bond; length as m-dashNP(double bond; length as m-dashS)(OR)2}Ph2]2 (R = Ph (2a), Et (2b)). The ruthenium(II) dimer [{Ru(η6-p-cymene)(μ-Cl)Cl}2] reacts with 2a,b to afford the cationic complexes [Ru(η6-p-cymene)(κ3-C,N,S-CH[P{double bond; length as m-dashNP(double bond; length as m-dashS)(OR)2}Ph2]2)]+ (R = Ph (3a), Et (3b)), via selective κ3-C,N,S-coordination of the bis(iminophosphorano)methanide anions to ruthenium. The structure of [Ru(η6-p-cymene)(κ3-C,N,S-CH[P{double bond; length as m-dashNP(double bond; length as m-dashS)(OEt)2}Ph2]2)][PF6] (3b) has been confirmed by single-crystal X-ray crystallography. Deprotonation of complexes 3a,b with NaH leads to the neutral carbene derivatives [Ru(η6-p-cymene)(κ2-C,N-C[P{double bond; length as m-dashNP(double bond; length as m-dashS)(OR)2}Ph2]2)] (R = Ph (4a), Et (4b)).