Abstract
Kinetic studies on the interconversion between trans-RhCl(FcC⋮CSiMe3)(PPri3)2 (2a) and trans-RhCl{CC(Fc)(SiMe3)}(PPri3)2 (3a) (Fc = ferrocenyl group) provided the following activation parameters for the forward and the backward reactions: ΔH⧧ = 19.8 ± 0.2 kcal mol-1 and ΔS⧧ = −4.8 ± 0.7 eu for 2a to 3a and ΔH⧧ = 22.7 ± 0.1 kcal mol-1 and ΔS⧧ = −8.6 ± 0.4 eu for 3a to 2a. The values are consistent with the isomerization mechanism via a sigmatropic 1,2-migration of the SiMe3 group.
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