Photooxygenations of PhSMe and Bu2S sensitized by N-methylquinolinium (NMQ+) and 9,10-dicyanoanthracene (DCA) in O2-saturated MeCN have been investigated by laser and steady-state photolysis. Laser photolysis experiments showed that excited NMQ+ promotes the efficient formation of sulfide radical cations with both substrates either in the presence or in absence of a cosensitizer (toluene). In contrast, excited DCA promotes the formation of radical ions with PhSMe, but not with Bu2S. To observe radical ions with the latter substrate, the presence of a cosensitizer (biphenyl) was necessary. With Bu2S, only the dimeric form of the radical cation, (Bu2S)2+*, was observed, while the absorptions of both PhSMe+* and (PhSMe)2+* were present in the PhSMe time-resolved spectra. The decay of the radical cations followed second-order kinetics, which in the presence of O2, was attributed to the reaction of the radical cation (presumably in the monomeric form) with O2-* generated in the reaction between NMQ* or DCA-* and O2. The fluorescence quenching of both NMQ+ and DCA was also investigated, and it was found that the fluorescence of the two sensitizers is efficiently quenched by both sulfides (rates controlled by diffusion) as well by O2 (kq = 5.9 x 10(9) M(-1) s(-1) with NMQ+ and 6.8 x 10(9) M(-1) s(-1) with DCA). It was also found that quenching of 1NMQ* by O2 led to the production of 1O2 in significant yield (PhiDelta = 0.86 in O2-saturated solutions) as already observed for 1DCA*. The steady-state photolysis experiments showed that the NMQ+- and DCA-sensitized photooxygenation of PhSMe afford exclusively the corresponding sulfoxide. A different situation holds for Bu2S: with NMQ+, the formation of Bu2SO was accompanied by that of small amounts of Bu2S2; with DCA, the formation of Bu2SO2 was also observed. It was conclusively shown that with both sensitizers, the photooxygenations of PhSMe occur by an electron transfer (ET) mechanism, as no sulfoxidation was observed in the presence of benzoquinone (BQ), which is a trap for O2-*, NMQ*, and DCA-*. BQ also suppressed the NMQ+-sensitized photooxygenation of Bu2S, but not that sensitized by DCA, indicating that the former is an ET process, whereas the second proceeds via singlet oxygen. In agreement with the latter conclusion, it was also found that the relative rate of the DCA-induced photooxygenation of Bu2S decreases by increasing the initial concentration of the substrate and is slowed by DABCO (an efficient singlet oxygen quencher). To shed light on the actual role of a persulfoxide intermediate also in ET photooxygenations, experiments in the presence of Ph2SO (a trap for the persulfoxide) were carried out. Cooxidation of Ph2SO to form Ph2SO2 was, however, observed only in the DCA-induced photooxygenation of Bu2S, in line with the singlet oxygen mechanism suggested for this reaction. No detectable amounts of Ph2SO2 were formed in the ET photooxygenations of PhSMe with both DCA and NMQ+ and of Bu2S with NMQ+. This finding, coupled with the observation that 1O2 and ET ph...
A series of aryl-substituted N-hydroxyphthalimides (X-NHPIs) containing either electron-withdrawing groups (4-CH(3)OCO, 3-F) or electron-donating groups (4-CH(3), 4-CH(3)O, 3-CH(3)O, 3,6-(CH(3)O)(2)) have been used as catalysts in the aerobic oxidation of primary and secondary benzylic alcohols. The selective formation of aromatic aldehydes was observed in the oxidation of primary alcohols; aromatic ketones were the exclusive products in the oxidation of secondary alcohols. O-H bond dissociation enthalpies (BDEs) of X-NHPIs have been determined by using the EPR radical equilibration technique. BDEs increase with increasing the electron-withdrawing properties of the aryl substituent. Kinetic isotope effect studies and the increase of the substrate oxidation rate by increasing the electron-withdrawing power of the NHPI aryl substituent indicate a rate-determining benzylic hydrogen atom transfer (HAT) from the alcohol to the aryl-substituted phthalimide-N-oxyl radical (X-PINO). Besides enthalpic effects, polar effects also play a role in the HAT process, as shown by the negative rho values of the Hammett correlation with sigma(+) and by the decrease of the rho values (from -0.54 to -0.70) by increasing the electron-withdrawing properties of the NHPI aryl substituent. The relative reactivity of 3-CH(3)O-C(6)H(4)CH(2)OH and 3,4-(CH(3)O)(2)-C(6)H(3)CH(2)OH, which is higher than expected on the basis of the sigma(+) values, the small values of relative reactivity of primary vs secondary benzylic alcohols, and the decrease of the rho values by increasing the electron-withdrawing properties of the NHPI aryl substituent, suggest that the HAT process takes place inside a charge-transfer (CT) complex formed by the X-PINO and the benzylic alcohol.
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