Electron Paramagnetic Resonance and Computational Studies of Radicals Derived from Boron-Substituted N-Heterocyclic Carbene Boranes. - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of the American Chemical Society Année : 2011

Electron Paramagnetic Resonance and Computational Studies of Radicals Derived from Boron-Substituted N-Heterocyclic Carbene Boranes.

Résumé

Fifteen second-generation NHC-ligated boranes with aryl and alkyl substituents on boron were prepared, and their radical chemistry was explored by electron paramagnetic resonance (EPR) spectroscopy and calculations. Hydrogen atom abstraction from NHC-BH(2)Ar groups produced boryl radicals akin to diphenylmethyl with spin extensively delocalized across the NHC, BH, and aryl units. All of the NHC-B*HAr radicals studied abstracted Br-atoms from alkyl bromides. Radicals with bulky N,N'-dipp substituents underwent dimerization about 2 orders of magnitude more slowly than first-generation NHC-ligated trihydroborates. The evidence favored head-to-head coupling yielding ligated diboranes. The first ligated diboranyl radical, with a structure intermediate between that of ligated diboranes and diborenes, was spectroscopically characterized during photolysis of di-t-butyl peroxide with N,N'-di-t-butyl-imidazol-2-ylidene phenylborane. The reactive site of B-alkyl-substituted NHC-boranes switched from the boron center to the alkyl substituent for both linear and branched alkyl groups. The β-borylalkyl radicals obtained from N,N'-dipp-substituted boranes underwent exothermic β-scissions with production of dipp-Imd-BH(2)* radicals and alkenes. The reverse additions of NHC-boryl radicals to alkenes are probably endothermic for alkyl-substituted alkenes, but exothermic for conjugated alkenes (addition of an NHC-boryl radical to 1,1-diphenylethene was observed). A cyclopropylboryl radical was observed, but, unlike other α-cyclopropyl-substituted radicals, this showed no propensity for ring-opening.

Domaines

Chimie organique
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Dates et versions

hal-00606475 , version 1 (06-07-2011)

Identifiants

Citer

John C Walton, Malika Makhlouf Brahmi, Julien Monot, Louis Fensterbank, Max Malacria, et al.. Electron Paramagnetic Resonance and Computational Studies of Radicals Derived from Boron-Substituted N-Heterocyclic Carbene Boranes.. Journal of the American Chemical Society, 2011, 133 (26), pp.10312-10321. ⟨10.1021/ja2038485⟩. ⟨hal-00606475⟩
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