New borylation methodologies have been reported recently, wherein diboron(4) compounds apparently participate in free radical couplings via the homolytic cleavage of the B–B bond. We report herein that bis-NHC adducts of the type (NHC)₂·B₂(OR)₄, which are thermally unstable and undergo intramolecular ring expansion reactions (RER), are sources of boryl radicals of the type NHC–BR₂˙, exemplified by Me₂Im^Me·Bneop˙ 1a (Me₂Im^Me = 1,3,4,5-tetramethyl-imidazolin-2-ylidene, neop = neopentylglycolato), which are formed by homolytic B–B bond cleavage. Attempts to apply the boryl moiety 1a in a metal-free borylation reaction by suppressing the RER failed. However, based on these findings, a protocol was developed using Me₂Im^Me·B₂pin₂3 for the transition metal- and additive-free boryl transfer to substituted aryl iodides and bromides giving aryl boronate esters in good yields. Analysis of the side products and further studies concerning the reaction mechanism revealed that radicals are likely involved. An aryl radical was trapped by TEMPO, an EPR resonance, which was suggestive of a boron-based radical, was detected in situ, and running the reaction in styrene led to the formation of polystyrene. The isolation of a boronium cation side product, [(Me₂Im^Me)₂·Bpin]⁺I⁻7, demonstrated the fate of the second boryl moiety of B₂pin₂. Interestingly, Me₂Im^Me NHC reacts with aryl iodides and bromides generating radicals. A mechanism for the boryl radical transfer from Me₂Im^Me·B₂pin₂3 to aryl iodides and bromides is proposed based on these experimental observations.