Hydride abstraction from N,N�-bis(adamantyl)-1-hydrido-1,3,2- benzodiazaborole with catalytic [Ph 3C][closo-CB 11H 6Br 6] resulted in a low yield of arene borylation and a major product derived from migration of both adamantyl groups to the arene backbone. In contrast, the related aryl-substituted diazaborole N,N�-(2,6-diisopropylphenyl)-1-bromo-1,3,2-diazaborole did not borylate benzene or toluene, being resistant to halide abstraction even with strong halide acceptors: e.g., [Et 3Si][closo-CB 11H 6Br 6]. The reactivity disparity arises from greater steric shielding of the boron p z orbital in the 2,6-diisopropylphenyl- substituted diazaboroles. Boron electrophiles derived from 1-chloro-1,3,2- benzodithiaborole ((CatS 2)BCl) are active for arene borylation, displaying reactivity between that of catecholato- and dichloro-boron electrophiles. [(CatS 2)B(NEt 3)][AlCl 4] is significantly less prone to nucleophile-induced transfer of halide from [AlCl 4] to boron compared to catecholato and dichloro borocations, enabling it to borylate arenes containing nucleophilic -NMe 2 moieties in high conversion (e.g., N,N,4-trimethylaniline and 1,8-bis(dimethylamino) naphthalene). Calculations indicate that the magnitude of positive charge at boron is a key factor in determining the propensity of chloride transfer from [AlCl 4] to boron on addition of a nucleophile. © 2012 American Chemical Society.