Further evidence of an inverted region in proton transfer within the benzophenone/substituted aniline contact radical ion pairs; importance of vibrational reorganization energy.
The dynamics of proton transfer within the triplet contact radical ion pair of a variety of substituted benzophenones with N,N-diethylaniline, N,N-dimethyl-p-toluinide, and N,N-diallylaniline are examined in solvents of varying polarity. The correlation of the rate constants with driving force reveal both a normal region and an inverted region providing support for the nonadiabatic nature of proton transfer within these systems. The reorganization of both the solvent and the molecular framework are central in governing the overall reaction dynamics.
Heeb
Libby R
LR
Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.
Peters
Kevin S
KS
D000498:Allyl Compounds / Q000737:chemistry; D000814:Aniline Compounds / Q000737:chemistry*; D001577:Benzophenones / Q000737:chemistry*; D004735:Energy Transfer; D005609:Free Radicals / Q000737:chemistry*; D008958:Models, Molecular; D011522:Protons; D012997:Solvents / Q000737:chemistry*; D013816:Thermodynamics; D014052:Toluidines / Q000737:chemistry; D014732:Vibration
D000498:Allyl Compounds; D000814:Aniline Compounds; D001577:Benzophenones; D005609:Free Radicals; D011522:Protons; D012997:Solvents; D014052:Toluidines; C047723:benzophenone; C015835:dimethyl-4-toluidine; C085691:2,6-diethylaniline