Reactions of PhSCH(2)Li and NCCH(2)Li with benzaldehyde and benzophenone: when does the mechanism change from ET to polar?

The carbonyl-carbon kinetic isotope effect (KIE) and the substituent effect were measured for the reaction of phenylthiomethyllithium (PhSCH(2)Li, 1) with benzaldehyde and benzophenone, and cyanomethyllithium (NCCH(2)Li, 2) with benzaldehyde, and the results were compared with those for other lithium reagents such as MeLi, PhLi, CH(2)=CHCH(2)Li, and CH(2)=C(OLi)C(CH(3))(3). It was previously shown that the reactions of MeLi, PhLi, and CH(2)=CHCH(2)Li proceed via a rate-determining electron transfer (ET) process whereas the reaction of lithium pinacolone enolate goes through the polar (PL) mechanism. The reaction of 1 with benzaldehyde gave no carbonyl-carbon KIE ((12)k/(13)k = 0.999 +/- 0.004), similar to that measured previously for the MeLi reaction with benzophenone ((12)k/(14)k = 1.000). The effect of substituents of the aromatic ring of benzaldehyde and benzophenone on the reactivity gave very small Hammett rho values of 0.17 +/- 0.03 and 0.26 +/- 0.05, respectively. These small rho values are again similar to that observed for the reaction of MeLi. Likewise the reactions of 2 with benzaldehydes gave small KIE and the rho value ((12)k/(13)k = 0.996 +/- 0.004, rho = 0.14 +/- 0.02). Dehalogenation and enone-isomerization probe experiments for 2 showed no evidence for the presence of radical-ion pair of sufficient lifetime during the course of the reaction. It is concluded that the reactions of 1 and 2 with the aromatic carbonyl compounds proceed via the electron transfer-radical coupling mechanism with rate-determining ET as in the reactions of MeLi, PhLi, and CH(2)=CHCH(2)Li.