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Electron Transfer and Polar Reactions of Cyclizable Anion Radicals: Structural Consequences of Orbital Selection Rules and Chain‐Length Constraints
Author(s) -
Sastry G. Narahari,
Reddy A. Chandrasekhar,
Shaik Sason
Publication year - 1995
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199514951
Subject(s) - chemistry , electron transfer , radical , ion , valence (chemistry) , ab initio , transition state , molecular orbital , computational chemistry , polar , valence bond theory , methylene , chemical physics , photochemistry , molecule , catalysis , physics , organic chemistry , astronomy
Transition states for electron transfer with strong bonding interactions are reported in the reactions of anion radicals 1 ( n = 2,3). The heights of the activation barriers for the substitution and electron transfer pathways leading to 2 and 3 , respectively, are a function of the length n of the methylene chain. This is predicted on the basis of orbital selection rules derived from valence bond configuration mixing analysis, and confirmed here by ab initio calculations.