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The ability of triplet nitrenes to abstract hydrogen atoms
Author(s) -
Sankaranarayanan Jagadis,
Rajam Sridhar,
Hadad Christopher M.,
Gudmundsdottir Anna D.
Publication year - 2010
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.1654
Subject(s) - chemistry , nitrene , hydrogen , photochemistry , computational chemistry , organic chemistry , catalysis
The enthalpies for H‐atom abstraction reactions by triplet imidogen as well as ethyl, alkoxycarbonyl, acyl, phenyl, and vinyl nitrenes were calculated using density functional theory calculations. These calculations show that H‐atom abstraction reactions are only feasible for triplet imidogen, alkoxycarbonyl, and acyl nitrenes in solution. The calculated charges on the N‐atoms ( Q NPA ) in the nitrene correlate with the magnitude of the transition state barrier for the H‐atom abstraction reactions from methanol as a model reactant. Electron‐withdrawing substituents on these nitrenes make them less stable but do not affect the transition state barrier significantly. Thus, as the electron deficiency of the N‐atom in the nitrenes is increased, the H‐atom abstraction reaction becomes more feasible. Copyright © 2010 John Wiley & Sons, Ltd.