The rate constants for the reduction of 2-butanone, methylacetoacetate, N,N-dimethylacetoacetamide, and a series of 4'- and 2'-substituted acetophenone derivatives by SmI2 were determined in dry THF using stopped-flow absorption decay experiments. Activation parameters for the electron-transfer processes in each series of compounds were determined by a temperature-dependence study over a range of 30 to 50 degreesC. Two types of reaction pathways are possible for these electron-transfer processes. One proceeds through coordination (Scheme 1) while the other involves chelation (Scheme 2). The results described herein unequivocally show that both coordination and chelation provide highly ordered transition states for the electron-transfer process but the presence of a chelation pathway dramatically increases the rate of the reduction of these substrates by SmI2. The ability of various functional groups to promote a chelated reaction pathway plays a crucial role in determining the rate of the reaction. Among the 2'-substituted acetophenone series, the presence of a fluoro, amino, or methoxy substituent enhances the rate of reduction compared to the 4'-analogues. In particular, the presence of a 2'-fluoro substituent on acetophenone provides a highly ordered transition state and considerably enhances the rate of ketone reduction.