Electron-Transfer Nucleophilic Substitution Reactions on Neopentyl- and Phenyl-Substituted Alkyl Chlorides. Effect of the Bridge Length on the Intramolecular Electron-Transfer Catalysis.

The nucleophilic substitution reaction of the chlorides RMe(2)CCH(2)Cl (R = Me, 4; Ph, 5a; PhCH(2), 5b) and their relative reactivities toward diphenyl phosphide ions were studied under irradiation in liquid ammonia. The relative reactivities determined were k(5a)()/k(4)() congruent with 9 and k(5b)()/k(4)() congruent with 0.85. These reactions are proposed to occur through the S(RN)1 mechanism. The higher reactivity of 5a is explained on the basis of its higher electron affinity due to the phenyl substitution and the efficient intramolecular electron transfer from this group to the C-Cl sigma bond (intra-ET catalysis). Although 5b also has a phenyl ring, its lower reactivity is ascribed to a decrease in the rate of the intra-ET by elongation of the bridge in one methylene unit. The relative reactivity of 5a versus 5b (k(5a)()/k(5b)() congruent with 6.4) is proposed to indicate the ratio of the intra-ET rates of the radical anions of both compounds. AM1 calculations performed on the system are in agreement with the experimental results.