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 M-3(mu-H)(3)(mu(3)-CBr)(CO)(9) (M = Ru, Os) to prepare the complexes M-3(mu-H)(3)(mu(3)-CC CR)(CO)9 [M = Ru, R = Ph 2, C CSiMe3 3, Fc 4, C CFc 6-Ru, C C[Ru(PPh3)(2)Cp] 8; M = Os, R = C CFc 6-Os, C CC CFc 7], Fc'{(mu(3)-C CC)Ru-3(mu-H)(3)(CO)(9)}(2) 5 and bis-cluster-capped carbon chain complexes {M-3(mu-H)(3)(CO)(9)}(2){mu(3):mu(3)-C(C C)(n)C} (M = Ru, n = 2 9, 3 10-Ru; M = Os, n = 3 10-Os) and {(L)(OC)(8)(mu-H)(3)M-3}C(C C)(n)C{Co-3(mu-dppm)(CO)(7)} (n = 1, M = Ru, L = CO 11, PPh3 12-Ru/P; n = 2. L = CO 12-Ru, PPh3 13; 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. (c) 2004 Elsevier B.V. All rights reserved.