169052-10-2Relevant articles and documents
Internal return in the photochemistry of ring-substituted 1-(1-naphthyl)ethyl esters of phenylacetic acid
Kim, J. M.,Pincock, J. A.
, p. 885 - 895 (2007/10/03)
The photochemistry in methanol of the esters 12a-d been studied in order to determine the importance of internal return of both ion pair and radical pair intermediates.The efficiency of internal return, determined by monitoring 18O exchange between the alcohol and carbonyl oxygens, was shown to be substituent dependent, varying from approximately 10percent for the 4,7-dimethoxy substrate to nearly 50percent for the 4-cyano case.The corresponding ground state solvolysis reactions gave about 10percent internal return and, within experimental error, were substituent independent.Internal return was also examined by racemization of the chiral center in 12a and 12d.In summary, these combined results reveal that internal return probably occurs mainly through a contact (not solvent-separated) radical pair.More important, internal return has little effect on previously calculated electron transfer rate constants for converting the radical pair to the ion pair.Therefore, the previously reported Marcus' correlations are valid.Key words: photochemistry of benzylic esters, internal return, photosolvolysis, electron transfer, radical pairs.
