Carebene and isocyanide ligation at ruthenium(II) with (η6-arene) and tethered phosphinopropylarene ligands

Reactions of [(η6-1,2,4,5-Me4C6H2)Ru(DPVP)Cl2] (DPVP=diphenylvinyl phosphine), with (trimethylsilyl)acetylene and phenylacetylene in the presence of NaPF6 in methanol gave the (methoxy)–alkylcarbene complexes [(η6-1,2,4,5-Me4C6H2)Ru(C (OMe)(R))(DPVP)(Cl)]PF6 (R=CH3, 1a; CH2Ph, 2a). Similarly, treatment of [(η6-1,2,4-Me3C6H25-CH2CH2CH2P(C6H5)2)RuCl2] with (trimethylsilyl)acetylene, phenylacetylene and 1,1-diphenylpropargyl alcohol in the presence of NaPF6 gave the tethered carbene complexes [(η6-1,2,4-Me3C6H25-CH2CH2CH2P(C6H5)2)Ru(C(OMe)(R))(Cl)]PF6 (R=CH3, 1b; CH2Ph, 2b; CHCPh2, 3b), respectively. The complexes, [(η6-arene)Ru(DPVP)Cl2] and [(η6-areneCH2CH2CH2P(C6H5)2)RuCl2] are shown to be useful catalyst precursors for the hydration of phenylacetylene to afford acetophenone. The complexes, [(η6-arene)Ru(DPVP)Cl2] (arene=1,3,5-Me3C6H31, p-MeC6H4CHMe22, 1,2,4,5-Me4C6H23 and Me6C64) react with excess phenyl-isocyanide and NaPF6 in methanol to produce [(η6-arene)Ru(DPVP)(CNPh)(Cl)]PF6 derivatives 1c–4c. The related tethered complexes 1d and 2d were prepared from [(η6-arene-CH2CH2CH2P(C6H5)2)RuCl2] by using the same methodology. All the complexes have been characterized spectroscopically and the crystal structures of some of them have been obtained.