Triruthenium clusters containing vinyl ligands:: synthesis and structure of Ru3(μ2-CO)2(CO)6[μ3-NS)(O)MePh](μ2-η1,η2-PhCH2C=CH2), Ru3(μ2-CO)(CO)7[μ3-NS(O)MePh](μ3-η1,η2-PrnC=CHPrn), Ru3(μ2-CO)(CO)7[μ3-NS(O)MePh](μ3-η1,η2-PhC=CHBun), and (μ2-H)Ru3(CO)6(μ2-η1,η2-PhC=CHPh)(μ3-η1,η2-PhCCPh)[μ3-η1,η2-NS(O)Me(C6H4)]

The electron-deficient cluster (mu(2)-H)Ru-3(CO)(9)[mu(3)-NS(O)MePh] (1) reacts with the terminal alkyne PhCH2C=CH to give the vinyl complex Ru-3(mu(2)-CO)(2)(CO)(6)[mu(3)-NS(O)MePh](mu(2)-eta(1),eta(2)-PhCH2C=CH2) (2). The analogous reaction with internal alkynes (RC=CR') affords the clusters Ru-3(mu(2)-CO)(CO)(7)[mu(3)-NS(O)MePh](mu(3)-eta(1),eta(2)-RC=CHR') (3: R = R' = Pr "; 4: R = Ph; R' = Bu ") in which the vinyl ligand has opened a Ru-Ru bond upon coordination the Ru-3 framework. In the case of diphenylacetylene, reaction with two equivalents of the alkyne, yields the vinyl-alkyne cluster (mu(2)-H)Ru-3(CO)(6)(mu(2)-eta(1),eta(2)-PhC=CHPh)(mu(3)-eta(1),eta(2)-PhC=CPh)[mu(3)-eta(1),eta(2)-NS(O)Me(C6H4)] (5) with ortho-metallation of the phenyl substituent of the sulfoximido cap. (C) 1997 Elsevier Science S.A.