SYNTHESIS AND CHARACTERIZATION OF DIPHENYLVINYLPHOSPHINE-SUBSTITUTED OSMIUM AND RUTHENIUM CARBONYL CLUSTERS - CRYSTAL AND MOLECULAR-STRUCTURES OF [OS-3(CO)(11)(PH(2)PCH=CH2)] AND [OS-3(MU-H)(CO)(9)(MU-PH(2)PCH=CH)]

Reaction of the activated clusters [Os-3(CO)(12-n)(NCMe)(n)](n = 1 or 2) with diphenylvinylphosphine (Ph(2)PCH-CH2) afforded [Os-3(CO)(12-n) (Ph(2)PCH=CH2)(n)](n = 11 or 22) in good yield. Addition of Ph(2)PCH=C H2 to [Os-3(mu-H)(2)(CO)(10)] resulted in the formation of [Os-3(mu-H) H(CO)(10)(Ph(2)PCH=CH2)]3. The ruthenium clusters [Ru-3(CO)(12-n)(Ph(2 )PCH=CH2)n](n = 14 or 25) have been synthesised by the reaction of [[R u-3(CO)(12)] With an excess of diphenylvinylphosphine in the presence of a catalytic amount of Na-Ph(2)CO. Thermolysis of 1 led to the forma tion of [Os-3(mu-H)(CO)(9)(mu(3)-Ph(2)PCH=CH)] 6 in which the vinyl mo iety has undergone beta elimination. Similarly, 4 and 5 are converted into [Ru-3(mu-H)(CO)(9)(mu(3)-Ph(2)PCH=CH)]7 and the known complex -3( mu-H)(CO)(8)(Ph(2)PCH=CH2)(mu(3)-Ph(2)PCH=CH)]8 under mild conditions (thermolysis or photolysis). No intermediate species could be detected during the formation of 6-8. All of the new clusters 2-7 have been fu lly characterised on the basis of their spectroscopic data and the mol ecular structures of 1 and 6 have been established by single-crystal X -ray analysis.