期刊
ORGANIC & BIOMOLECULAR CHEMISTRY
卷 4, 期 15, 页码 2928-2931出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/b605362a
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The flexible 3 and rigid cyclic viologens 4, diquarternary salts of 2,2'-bipyridine and 1, 1 0-phenanthroline, respectively, were treated with tributylphosphine (1) in acetonitrile containing a large amount of methanol under an argon atmosphere. A single electron transfer (SET) easily occurred from the latter to the former, the SET to 4 being 10(5)-10(6) times faster than the SET to 3. The reorganization energy 2 for the latter SET is thought to be larger than that for the former SET, because 3 undergoes a structural change upon the one-electron reduction to its radical cation, whereas the one-electron reduction of 4 takes place without a structural change. Taking into account the difference in lambda, and also taking into account the bond formation energy brought about by the follow-up reaction of the phosphine radical cation 1(.+) with methanol, the observed kinetics were well interpreted in terms of the Marcus theory.
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