Abstract
Abstract The kinetics for isomerization of HRu3 (μ3-η3-EtSCCMeCMe)(CO)9 TO Ru3(μ-SEt) (μ3-η3-CCMeCHMe)(CO)9, were determined. The overall process involves C[sbnd]H elimination, C[sbnd]S and Ru[sbnd]Ru bond cleavage and Ru2(μ-S) bond formation. Activation parameters were determined from the temperature dependence (ΔH‡ = 127(3) kJ/mol, ΔS‡= 56(11) J/mol-K) and from the pressure dependence (0[sbnd]207 MPa, ΔV‡ 0 +12.7(1.1) cm3/mol, Δβ‡ = +0.037(0.012) cm3/(mol-MPa)) of the rate constant. The data are consistent with an intramolecular reaction involving significant metal-metal or carbon-sulfur bond cleavage in the transition state. The activation volume is too large to be accommodated by C[sbnd]H elimination alone and CO dissociation is not involved.
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