Preparation of new acetylide and vinylidene complexes of ruthenium

Monoacetylide RuCl(C=CR)P-4 complexes (R = Ph, 4-MeC6H4, 1,4-C6H4C=CH, SiMe3, Bu' or COOMe; P=P(OEt)(3) or P(OMe)(3)) were prepared by allowing RuCl2P4 to react with terminal alkynes RC=CH in the presence of an excess of NEt3. Dinuclear compounds [{Ru[P(OEt)(3)](5)}(2)(mu-1,4-C=CC6H4C=C)]Y-2 (Y = PF6 or BPh4) were also prepared from the reaction of RuCl2P4 with 1,4-HC=CC6H4C=CH. Treatment of RuCl2P4 with Li+ [1,4-HC=CC6H4C=C](-) afforded bis(alkynyl) Ru(1,4-C=CC6H4C=CH)(2)P-4 [P = P(OEt)(3), P(OMe)(3) or PPh(OEt)(2)] derivatives. Protonation reactions of monoacetylides RuCl(C=CR)P-4 with CF3SO3H led to vinylidene [RuCl{=C=C(H)R}P-4]CF3SO3 [R = Ph, 4-MeC6H4 or 1,4-C6H4C=CH; P = P(OEt)(3) or P(OMe)(3)] complexes, which were fully characterised by IR and H-1-, P-31- and C-13-NMR spectra. (C) 1999 Elsevier Science S.A. All rights reserved.