Construction of carbon chains on ruthenium and osmium carbonyl clusters

We have used the elimination of AuX(PR3) (X = halide, R = Ph, tol) that occurs in reactions of alkynylgold(I)–phosphine complexes with M3(μ-H)3 (μ3-CBr) (CO)9 (M = Ru, Os) to prepare the complexes M3(μ-H)3(μ3-CCtriple bond; length of mdashCR)(CO)9 [M = Ru, R = Ph 2, Ctriple bond; length of mdashCSiMe33, Fc 4, Ctriple bond; length of mdashCFc 6-Ru, Ctriple bond; length of mdashC[Ru(PPh3)2Cp] 8; M = Os, R = Ctriple bond; length of mdashCFc 6-Os, Ctriple bond; length of mdashCCtriple bond; length of mdashCFc 7], Fc′{(μ3-Ctriple bond; length of mdashCC)Ru3(μ-H)3(CO)9}25, and bis-cluster-capped carbon chain complexes {M3(μ-H)3(CO)9}2{μ3:μ3-C(Ctriple bond; length of mdashC)nC} (M = Ru, n = 2 9, 3 10-Ru; M = Os, n = 3 10-Os) and {(L)(OC)8(μ-H)3M3}C(Ctriple bond; length of mdashC)nC{Co3(μ-dppm)(CO)7} (n = 1, M = Ru, L = CO 11, PPh312-Ru/P; n = 2, L = CO 12-Ru, PPh313; M = Os, L = CO 12-Os) in good to excellent yields. X-ray structural determinations of 2–5, 6-Ru, 6-Os, 7, 9, 11, 12-Ru, 12-Os and 12-Ru/P are reported.