SYNTHESES AND REACTIONS OF THE CARBYNE COMPLEXES, M(CR)CL(CO)(PPH3)(2) (M = RU, OS R = 1-NAPHTHYL, 2-NAPHTHYL) - THE CRYSTAL-STRUCTURES OF [OS(C-1-NAPHTHYL)(CO)(2)(PPH3)(2)]CLO4, OS(=CH-2-NAPHTHYL)CL-2(CO)(PPH3)(2), AND OS(2-NAPHTHYL)CL(CO)(2)(PPH3)(2)

Treatment of the dichlorocarbene-containing complex, Os(=CCl2)Cl-2(CO) (PPh3)(2) with two equivalents of 1-naphthyllithium or two equivalents of 2-naphthyllithium in the presence of N,N,N',N'-tetramethylethylene diamine (tmeda) gives the corresponding carbyne-containing complexes O s(=CR)Cl(CO)(PPh3)(2) (R = 1-naphthyl (1); R = 2-naphthyl (2)). Simila r treatment of Ru(=CCl2)Cl-2(CO)(PPh3)(2) with two equivalents of phen yllithium or 1-naphthyllithium yields Ru(=CR)Cl(CO)(PPh3)(2) (R = Ph ( 3); R = 1-naphthyl (4)). When 1, 2, 3 and 4 are carbonylated in the pr esence of AgClO4 the corresponding carbyne-containing cations [M(=CR)( CO)(2)(PPh3)(2)]ClO4 are formed (M=Os, R= 1-naphthyl (5); M=Os, R= 2-n aphthyl (6); M=Ru, R=Ph (7); M=Ru, R= 1-naphthyl (8)). When Ru(=CPh)Cl (CO)(PPh3)(2) is added to an acetonitrile solution containing two equi valents of AgClO4 in the absence of CO the complex [Ru(=CPh{AgOClO3})( NCMe)(CO)(PPh3)(2)]ClO4 (9) can be isolated. Addition of LiCl to 9 yie lds the complex Ru(=CPh{AgCl})Cl(CO)(PPh3)(2) (10). The acids HX react with the neutral carbyne complexes 1, 2, 3 or 4 to form the correspon ding carbene complexes M(=CHR)ClX(CO)(PPh3)(2) (M = Os, R = 1-naphthyl , X = Cl (11); M = Os, R = 2-naphthyl, X = Cl (12); M = Ru, R = Ph, X = Cl (13); M = Ru, R = 1-naphthyl, X = Cl (14); M = Os, R = 1-naphthyl , X = ClO4 (15); M = Os, R = 1-naphthyl, X = F (16)). Treatment of com plexes 1 or 2 with PhICl2, leads to corresponding monochlorocarbene-co ntaining complexes Os(=CClR>Cl-2(CO)(PPh3)(2) (R = 1-naphthyl (17); R = 2-naphthyl (18)) which subsequently rearrange on addition of aqueous base to give the sigma-naphthyl, dicarbonyl complexes OsRCl(CO)(2)(PP h3)(2) (R = 1-naphthyl (19); R = 2-naphthyl (20)). The single crystal X-ray structures of [Os(=C-1-naphthyl)(CO)(2)(PPh3)(2)]ClO4, Os(=CH-2- naphthyl)Cl-2(CO)(PPh3)(2), and Os(2-naphthyl)Cl(CO)(2)(PPh3)(2) have been determined. (C) 1998 Elsevier Science S.A.