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Comparison of the cleavage reactions of αnitrocumene radical anion and α, p –dinitrocumene radical anion
Author(s) -
Wu Fangfang,
Guarr Thomas F.,
Guthrie Robert D.
Publication year - 1992
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610050103
Subject(s) - chemistry , heterolysis , radiolysis , homolysis , ion , radical ion , photochemistry , reaction rate constant , dissociation (chemistry) , radical , medicinal chemistry , cyclic voltammetry , organic chemistry , electrochemistry , kinetics , electrode , catalysis , physics , quantum mechanics
The rates of loss of NO 2 − from the radical anions of 2‐(4‐nitrophenyl)‐2‐nitropropane (α, p ‐dinitrocumene) and 2‐phenyl‐2‐nitropropane (α‐nitrocumene) were compared by three different methods. The rate constant for the apparently heterolytic process ( D N ) undergone by the radical anion of the dinitrocumene was measured by pulse radiolysis to be 2 × 10 3 s −1 in dimethylformide at 25°C. This value is in reasonable agreement with values estimated from an indirect chemical method and from cyclic voltammetry at low temperature. The rate for the formally homolytic dissociation process ( D R ) undergone by the radical anion of the mononitrocumene could not be determined by pulse radiolysis but could be shown to be between 50 and 1000 times faster than the dinitro case using the other two methods. Possible reasons for the faster rate for the D R process are discussed with reference to related systems for which the D R process had been found to be unexpectedly slow.