TY - JOUR ID - pittir16322 UR - http://d-scholarship-dev.library.pitt.edu/16322/ IS - 26 A1 - Walton, JC A1 - Brahmi, MM A1 - Monot, J A1 - Fensterbank, L A1 - Malacria, M A1 - Curran, DP A1 - Lac?te, E Y1 - 2011/07/06/ N2 - 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 - BH2Ar 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 ?-borylalkyl radicals obtained from N,N?-dipp-substituted boranes underwent exothermic ?-scissions with production of dipp-Imd - BH2· 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 ?-cyclopropyl-substituted radicals, this showed no propensity for ring-opening. © 2011 American Chemical Society. JF - Journal of the American Chemical Society VL - 133 SN - 0002-7863 TI - Electron paramagnetic resonance and computational studies of radicals derived from boron-substituted N-heterocyclic carbene boranes SP - 10312 AV - public EP - 10321 ER -