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• W2000434982 abstract "The kinetics of the isomerizations of (μ-H)3Ru3(μ3-CCO2Me)(CO)9 to (μ-H)2Ru3(μ3-η2-CHCO2Me)(CO)9 and of (μ-H)3Ru3(μ3-CSEt)(CO)9 to (μ-H)Ru3(μ3-η2-CH2SEt)(CO)9, including the measurements of activation volumes, are reported. An earlier study of reductive elimination of CH3X from H3Ru3(μ3-CX)(CO)9 found that the reaction was promoted by CO for X = Ph, Cl, and Et and was unaffected by CO pressure for X = CO2Me. The activation volume ΔV⧧ for the intramolecular isomerization of (μ-H)3Ru3(μ3-CCO2Me)(CO)9 to (μ-H)2Ru3(μ3-η2-CHCO2Me)(CO)9 was determined to be −0.3(0.7) cm3/mol at 57.0 °C. For the isomerization of (μ-H)3Ru3(μ3-CSEt)(CO)9 to (μ-H)Ru3(μ3-η2-CH2SEt)(CO)9, the rate is inhibited by CO; activation parameters (ΔH⧧=121(3) kJ/mol, ΔS⧧= +36(10) J/(mol K), ΔV⧧= +22.0(1.4) cm3/mol) are consistent with a mechanism involving reversible CO dissociation prior to the rate-determining step but following an intramolecular rearrangement. The change in mechanism of reductive elimination of a C−H bond from CO associative to CO independent to CO dissociative is due to anchimeric assistance by the methylidyne substituent. These results may have relevance to C−H formation occurring on metal surfaces." @default.
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• W2000434982 date "1996-07-23" @default.
• W2000434982 modified "2023-10-03" @default.
• W2000434982 title "Kinetics and Mechanism of Reductive Elimination of C−H Bonds from (μ-H)₃Ru₃(μ₃-CX)(CO)₉ Revisited: CO Associative, CO Independent, or CO Dissociative?" @default.
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• W2000434982 doi "https://doi.org/10.1021/om960154g" @default.
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