Reactions of thiol-functionalized silsesquioxanes with metal carbonyl clusters:: syntheses and characterization of [Si8O12(Prn)7{(μ2-SC3H6)M3(μ-H)(CO)10}](M = Ru, Os; Prn = C5H7) [Si8O12(Prn)6{(μ2-SC3H6)Ru3(μ-H)(CO)10}2] and [Si8O12(C3H6SH)x{(μ2-SC3H6)Ru3(μ-H)(CO)10}8-x](x = 6, 0)

The thiol-functionalised silsesquioxanes, [Si8O12(Pr-n)(7)(C3H6SH)], 1, and [Si8O12(Pr-n)(6){o-(C3H6SK)(2)}], 2) (Pr-n = C3H7) readily react with the activated metal clusters [M-3(CO)(10)(NCMe)(2)] (M = Ru, Os) to form cluster-substituted silsesquioxanes. The compounds [Si8O12(Pr-n)(7){(mu(2)-SC3H6)M-3(mu-H)(CO)(10))] (M = Ru, 4; M = Os, 5) and [Si8O12(Pr-n)(6)(o-(mu(2)-SC3H6)Ru-3(mu-H)(CO)(10))(2)] 6 have been prepared and characterized. The octa-substituted silsesquioxane, [Si8O12(C3H6SH)(8)], 3, may be partially or completely substituted at its thiol functionalities depending on the reaction stoichiometry employed; [Si8O12(C3H6SH)(6){(mu(2)-SC3H6)Ru-3(mu-H)(CO)(10)}(2)], 7, and [Si8O12{(mu(2)-SC3H6)Ru-3(mu-H)(CO)(10)}(8)], 8, have been prepared. (C) 1998 Elsevier Science S.A.