The N-methylquinolinium tetrafluoroborate (NMQ+)-sensitized photolysis of the erythro-1,2- diphenyl-2-arylsulfanylethanols 1-3 (1, aryl ) phenyl; 2, aryl ) 4-methylphenyl; 3, aryl ) 3-chlorophenyl) has been investigated in MeCN, under laser flash and steady-state photolysis. Under laser irradiation, the formation of sulfide radical cations of 1-3, in the monomeric (ìmax ) 520- 540 nm) and dimeric form (ìmax ) 720f800 nm), was observed within the laser pulse. The radical cations decayed by first-order kinetics, and under nitrogen, the formation of ArSCH¥Ph (ìmax ) 350-360 nm) was clearly observed. This indicates that the decay of the radical cation is due to a fragmentation process involving the heterolytic C-C bond cleavage, a conclusion fully confirmed by steady-state photolysis experiments (formation of benzaldehyde and the dimer of the R-arylsulfanyl carbon radical). Whereas the fragmentation rate decreases as the C-C bond dissociation energy (BDE) increases, no rate change was observed by the replacement of OH by OD in the sulfide radical cation (kOH/kOD ) 1). This suggests a transition state structure with partial C-C bond cleavage where the main effect of the OH group is the stabilization of the transition state by hydrogen bonding with the solvent. The fragmentation rate of 2-hydroxy sulfanyl radical cations turned out to be significantly slower than that of nitrogen analogues of comparable reduction potential, probably due to a more efficient overlap between the SOMO in the heteroatom and the C-C bond ó-orbital in the second case. The fragmentation rates of 1+¥-3+¥ were found to increase by addition of a pyridine, and plots of kbase against base strength were linear, allowing calculation of the â Brønsted values, which were found to increase as the reduction potential of the radical cation decreases, â ) 0.21 (3+¥), 0.34 (1+¥), and 0.48 (2+¥). The reactions of 1+¥ exhibit a deuterium kinetic isotope effect with values that increase as the base strength increases: kOH/kOD ) 1.3 (pyridine), 1.9 (4-ethylpyridine), and 2.3 (4-methoxypyridine). This finding and the observation that with the above three bases the rate decreases in the order 3+¥ > 1+¥ > 2+¥, i.e., as the C-C BDE increases, suggest that C-C and O-H bond cleavages are concerted but not synchronous, with the role of OH bond breaking increasing as the base becomes stronger (variable transition state). It is probable that, with the much stronger base, 4-(dimethylamino)pyridine, a change to a stepwise mechanism may occur where the slow step is the formation of a radical zwitterion that then rapidly fragmentates to products.
Steady State and Laser Flash Photolysis Study of the Carbon-Carbon Bond Fragmentation Reactions of 2-Arylsulfanyl Alcohol Radical Cations
DEL GIACCO, Tiziana;ELISEI, Fausto;
2004
Abstract
The N-methylquinolinium tetrafluoroborate (NMQ+)-sensitized photolysis of the erythro-1,2- diphenyl-2-arylsulfanylethanols 1-3 (1, aryl ) phenyl; 2, aryl ) 4-methylphenyl; 3, aryl ) 3-chlorophenyl) has been investigated in MeCN, under laser flash and steady-state photolysis. Under laser irradiation, the formation of sulfide radical cations of 1-3, in the monomeric (ìmax ) 520- 540 nm) and dimeric form (ìmax ) 720f800 nm), was observed within the laser pulse. The radical cations decayed by first-order kinetics, and under nitrogen, the formation of ArSCH¥Ph (ìmax ) 350-360 nm) was clearly observed. This indicates that the decay of the radical cation is due to a fragmentation process involving the heterolytic C-C bond cleavage, a conclusion fully confirmed by steady-state photolysis experiments (formation of benzaldehyde and the dimer of the R-arylsulfanyl carbon radical). Whereas the fragmentation rate decreases as the C-C bond dissociation energy (BDE) increases, no rate change was observed by the replacement of OH by OD in the sulfide radical cation (kOH/kOD ) 1). This suggests a transition state structure with partial C-C bond cleavage where the main effect of the OH group is the stabilization of the transition state by hydrogen bonding with the solvent. The fragmentation rate of 2-hydroxy sulfanyl radical cations turned out to be significantly slower than that of nitrogen analogues of comparable reduction potential, probably due to a more efficient overlap between the SOMO in the heteroatom and the C-C bond ó-orbital in the second case. The fragmentation rates of 1+¥-3+¥ were found to increase by addition of a pyridine, and plots of kbase against base strength were linear, allowing calculation of the â Brønsted values, which were found to increase as the reduction potential of the radical cation decreases, â ) 0.21 (3+¥), 0.34 (1+¥), and 0.48 (2+¥). The reactions of 1+¥ exhibit a deuterium kinetic isotope effect with values that increase as the base strength increases: kOH/kOD ) 1.3 (pyridine), 1.9 (4-ethylpyridine), and 2.3 (4-methoxypyridine). This finding and the observation that with the above three bases the rate decreases in the order 3+¥ > 1+¥ > 2+¥, i.e., as the C-C BDE increases, suggest that C-C and O-H bond cleavages are concerted but not synchronous, with the role of OH bond breaking increasing as the base becomes stronger (variable transition state). It is probable that, with the much stronger base, 4-(dimethylamino)pyridine, a change to a stepwise mechanism may occur where the slow step is the formation of a radical zwitterion that then rapidly fragmentates to products.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
