Activation of alkynes by {[Cp∗Ru(CO)(PMeiPr2)]+}: X-ray crystal structures of image and image

The complex View the MathML source[Cp∗Ru{OCMe2}(CO)(PMeiPr2)][BAr4′](2,Ar4′=3,5-C6H3(CF3)2) reacts with HCtriple bond; length of mdashCPh at −40 °C in CD2Cl2 furnishing the π-alkyne adduct View the MathML source[Cp∗Ru(η2-HCCPh)(CO)(PMeiPr2)][BAr4′] (3), which rearranges to the vinylidene complex View the MathML source[Cp∗RuCCHPh(CO)(PMeiPr2)][BAr4′] (4a) when the temperature is raised to 25 °C. View the MathML source[Cp∗RuCCHR(CO)(PMeiPr2)][BAr4′] (R = Ph 4a, tBu4b, H 4c) were obtained by reaction of [Cp∗RuCl(CO)(PMeiPr2)] (1) with View the MathML sourceNaBAr4′ and alkyne in fluorobenzene. Addition of water to the vinylidene complexes leads to the dicarbonyl View the MathML source[Cp∗Ru(CO)2(PMeiPr2)][BAr4′] (5), whereas deprotonation yields neutral σ-alkynyl complexes [Cp∗Ru(Ctriple bond; length of mdashCR)(CO)(PMeiPr2)] (R = tBu 6b, H 6c). The allenylidene complex View the MathML source[Cp∗RuCCCPh2(CO)(PMeiPr2)][BAr4′] (7) was prepared by reaction of 1 with HCtriple bond; length of mdashCC(OH)Ph2 and View the MathML sourceNaBAr4′ in fluorobenzene.