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Effects of CF 3 groups and charged substituents on singlet carbene stabilities–a density functional theory study
Author(s) -
Song MyoungGeun,
Sheridan Robert S.
Publication year - 2011
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.1913
Subject(s) - carbene , chemistry , singlet state , trifluoromethyl , polar effect , cationic polymerization , reactivity (psychology) , density functional theory , natural bond orbital , photochemistry , ground state , computational chemistry , catalysis , organic chemistry , atomic physics , alkyl , medicine , physics , excited state , alternative medicine , pathology
B3LYP calculations indicate that substitution of a trifluoromethyl group for hydrogen stabilizes singlet versus triplet carbene states by a small, but systematic amount. Geometry and natural bond orbital analysis suggests that this energy lowering is due to rehybridization at the carbenic centers induced by the strong inductive electron‐withdrawing effect of a CF 3 group. The trifluoromethyl group also increases the electron affinity of the carbenes, consistent with the observed increased reactivity. Calculations also indicate that more strongly electron‐withdrawing ammonium cationic ligands have an even more profound singlet stabilizing effect, suggesting a new type of ground‐state singlet carbene. Copyright © 2011 John Wiley & Sons, Ltd.