Exchange barriers solvent effect

The reader is also referred to the innovative nonphotochemical electron transfer studies of Weaver et al. [147], These authors have been exploring dynamical solvent effects on ground state self-exchange kinetics for or-ganometallic compounds. This work has explored many aspects of solvent control on intermediate barrier electron transfer reactions, including the effect on a distribution of solvation times. The experimental C(t) data on various solvents have been incorporated into the theoretical modeling of the ground state electron transfer reactions studied by Weaver et al. [147]. 

In view of results obtained later,65,66 (see following Section III.A.4) it now appears that the solvent effect is also to weaken (and polarize) the Si-Cl bond and facilitate its ionization. The substantially lower-barrier exchange process in CDC13 and CD2C12 may involve, in addition to the (X, Cl)-twist mechanism, ionization of the Si-Cl bond followed by re-entry of the chloride to a different position. 

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