期刊
INORGANIC CHEMISTRY
卷 49, 期 8, 页码 3685-3687出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic100143s
关键词
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资金
- U.S. National Institutes of Health [GM50422]
- Natural Sciences and Engineering Research Council of Canada [NSERC PGS-D2]
The transfer of a proton and an electron from the hydroxylamine 1-hydroxyl-2,2,6,6-tetramethylpiperidine (TEMPOH) to [Co-III(Hbim)(H(2)bim)(2)](2+) (H(2)bim = 2,2'-biimidazoline) has an overall driving force of Delta G degrees = -3.0 +/- 0.4 kcal mol(-1) and an activation barrier of Delta G double dagger = 21.9 +/- 0.2 kcal mol(-1). Kinetic studies implicate a hydrogen-bonded precursor complex at high [TEMPOH], prior to proton-electron (hydrogen-atom) transfer. In the reverse direction, [Co-II(H(2)bim)(3)](2+) + TEMPO, a similar successor complex was not observed, but upper and lower limits on its formation have been estimated. The energetics of formation of these encounter complexes are the dominant contributors to the overall energetics in this system: Delta G degrees' for the proton-electron transfer step is only -0.3 +/- 0.9 kcal mol(-1). Thus, formation of the precursor and successor complexes can be a significant component of the thermochemistry for intermolecular proton electron transfer, particularly in the low-driving-force regime, and should be included in quantitative analyses.
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