期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 139, 期 26, 页码 9010-9018出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b04232
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资金
- Robert A. Welch Foundation [B0027]
- National Science Foundation [CHE-1305872]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1305872] Funding Source: National Science Foundation
Experimental heats of formation and enthalpies obtained from G4 calculations both find that the resonance stabilization of the two unpaired electrons in triplet O-2, relative to the unpaired electrons in two hydroxyl radicals, amounts to 100 kcal/mol. The origin of this huge stabilization energy is described within the contexts of both molecular orbital (MO) and valence-bond (VB) theory. Although O-2 is a triplet diradical, the thermodynamic unfavorability of both its hydrogen atom abstraction and oligomerization reactions can be attributed to its very large resonance stabilization energy. The unreactivity of O-2 toward both these modes of self-destruction maintains its abundance in the ecosphere and thus its availability to support aerobic life. However, despite the resonance stabilization of the pi system of triplet O-2, the weakness of the O-O sigma bond makes reactions of O-2, which eventually lead to cleavage of this bond, very favorable thermodynamically.
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