Oligomerisation of alkynes at a pentamethylcyclopentadienylruthenium centre †

Abstract
Reactions between the neutral vinylidene RuCl(CCHPh)(PPh3)Cp* 2 and AgCCCO2Me gave Ru{η1-C(CCPh) CHC(O)OMe-O}(PPh3)Cp* 3, while either LiCCPh or HCCPh/NaOMe afforded the known Ru{η3-PhCHCHC CPh(CCPh)}(PPh3)Cp* 1. Similarly, RuCl{CCH(CO2Me)}(PPh3)Cp* 4 reacted with HCCPh/NaOMe to give Ru{η3-CH(CO2Me)CHCCPh(CCCO2Me)}(PPh3)Cp* 5. Complex 3 reacted with HCCCO2R (R = Me or Et) to give the 1,3,4,5-tetraen-1-yls Ru{η12-C(CO2R)CHCPhCCCH(CO2Me)}(PPh3)Cp* (R = Me 6 or Et 7)] and with HCCSiMe3 to give a mixture of Ru{η3-CH(CO2Me)C(CHCHSiMe3)CCPhCCSiMe3}(PPh3)Cp* 8 and Ru{η3-CH(CO2Me)CHCCPh(CCSiMe3)}(PPh3)Cp* 9. Crystal structures of 1, 3 and 5–8 were determined. These reactions provide routes to the stepwise formation of novel non-cyclic oligomers of 1-alkynes, with 8 containing the first example derived from four alkynes.

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