Syntheses and reactions of ruthenium complexes containing C6 and C8 chains

Reactions of {Cp(Ph3P)2Ru}2{μ-(CC)n} (n=3, 4) with C2(CN)4, dicobalt carbonyls and Fe2(CO)9 are described. For n=3, the central CC triple bond is attacked by the metal carbonyls, giving {Ru(PPh3)2Cp}2{μ-CCC2[Co2(CO)6]CC} (4), {Ru(PPh3)2Cp}2{μ-CCC2[Co2(μ-dppm)(CO)4]CC} (5) and Fe3{μ3-CCC[Ru(PPh3)2Cp]}2(CO)9 (7). For n=4, the first bis-adduct with tcne is described, while the metal carbonyls gave {Ru(PPh3)2Cp}2{μ-CCC2[Co2(μ-dppm)(CO)4]CCCC} (6) and Fe3{μ3-CCC[Ru(PPh3)2Cp]}{μ3-CCCCC[Ru(PPh3)2Cp]}(CO)9 (8). While the usual bending of the carbon chain is found in the dicobalt complexes, reactions with the iron carbonyl result in cleavage of a CC triple bond to give CFe3C clusters. The molecular structures of 4 and 7 have been determined.