Synthesis and characterisation of diphenylvinylphosphine-substituted osmium and ruthenium carbonyl clusters; crystal and molecular structures of [Os3(CO)11(Ph2PCH
CH2)] and [Os3(µ-H)(CO)9(µ-Ph2PCH
CH)]
Abstract
Reaction of the activated clusters [Os3(CO)12 –n(NCMe)n](n= 1 or 2) with diphenylvinylphosphine (Ph2PCHCH2) afforded [Os3(CO)12 –n(Ph2PCH
CH2)n](n= 1 1 or 2 2) in good yield. Addition of Ph2PCH
CH2 to [Os3(µ-H)2(CO)10] resulted in the formation of [Os3(µ-H)H(CO)10(Ph2PCH
CH2)]3. The ruthenium clusters [Ru3(CO)12 –n(Ph2PCH
CH2)n](n= 1 4 or 2 5) have been synthesised by the reaction of [Ru3(CO)12] with an excess of diphenylvinylphosphine in the presence of a catalytic amount of Na–Ph2CO. Thermolysis of 1 led to the formation of [Os3(µ-H)(CO)9(µ3-Ph2PCH
CH)]6 in which the vinyl moiety has undergone β elimination. Similarly, 4 and 5 are converted into [Ru3(µ-H)(CO)9(µ3-Ph2PCH
CH)]7 and the known complex [Ru3(µ-H)(CO)8(Ph2PCH
CH2)(µ3-Ph2PCH
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 fully characterised on the basis of their spectroscopic data and the molecular structures of 1 and 6 have been established by single-crystal X-ray analysis.