Oxidative addition of the C-O bond in L2PhB: (L=oxazol-2-ylidene) to an AlI center induced ring expansion of an oxazol-2-ylidene ring, affording a unique organoboron species formally involving either an Al, N, O mixed heterocyclic carbene or anionic (amino)(boryl)carbene fragment. Ring expansion of an oxazol-2-ylidene in L2PhB (L=oxazol-2-ylidene) through cleavage of the C-O bond by AlI resulted in the formation of a unique organoboron species formally involving either an Al, N, O mixed heterocyclic carbene or an anionic (amino)(boryl)carbene fragment. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.