Why Are Nitrenes More Stable than Carbenes? An Ab Initio Study
Journal of the American Chemical Society1998Vol. 120(14), pp. 3499–3503
Citations Over TimeTop 10% of 1998 papers
Abstract
High level ab initio calculations find that nitrenes are more stable than carbenes, as indicated by the computed enthalpy differences of 25−26 kcal/mol between triplet phenylnitrene and the isomeric triplet pyridylcarbenes. More generally, the greater thermodynamic stability of nitrenes manifests itself in the finding that the N−H bond dissociation energies (BDEs) of aminyl radicals are approximately 20 kcal/mol lower than the C−H BDEs of analogous alkyl radicals. The greater thermodynamic stability of nitrenes, relative to carbenes, is attributed to the large amount of 2s character in the orbital that is occupied by the lone pair of electrons in nitrenes.
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