Direct Observation of Ultrafast Decarboxylation of Acyloxy Radicals via Photoinduced Electron Transfer in Carboxylate Ion Pairs.

Charge-transfer (CT) photoactivation of the electron donor-acceptor salts of methylviologen (MV(2+)) with carboxylate donors (RCO(2)(-)) including benzilates [Ar(2)C(OH)CO(2)(-)] and arylacetates (ArCH(2)CO(2)(-)) leads to transient [MV(*)(+), RCO(2)(*)] radical pairs. Femtosecond time-resolved spectroscopy reveals that the photogenerated acyloxy radicals (RCO(2)(*)) rapidly lose carbon dioxide by C-CO(2) bond cleavage, in competition with back-electron transfer to restore the original ion pair, [MV(2+), RCO(2)(-)]. The decarboxylation rate constants for ArCH(2)CO(2)(*) lie in the range (1-2) x 10(9) s(-)(1), in agreement with previous reports. In striking contrast, the C-CO(2) bond scission in Ar(2)C(OH)CO(2)(*) occurs within a few picoseconds (k(CC) = (2-8) x 10(11) s(-)(1)). The rate constants for decarboxylation of these donors approach those of barrier-free unimolecular reactions. Thus, real-time monitoring of the decarboxylation of benziloxy radicals represents the means for the direct observation of the transition state for C-C bond scission.