Transition-metal boryl complexes of the form Cp‘Fe(CO)LBcat and (CO)5MBcat, where Cp‘ = C5H5, C5Me5, M = Mn, Re, L = CO, PMe3, and cat = 1,2-O2C6H4, were synthesized by reaction of ClBcat with [Cp‘Fe(CO)L]- or [M(CO)5]-. X-ray crystal structures of CpFe(CO)2Bcat, Cp*Fe(CO)2Bcat, and (CO)5MnBcat were obtained. Upon irradiation, these metal boryl complexes reacted with arenes and alkenes to form aryl- and vinylboronate ester products in moderate to high yields. Monosubstituted arenes with methyl, chloro, trifluoromethyl, methoxy, and dimethylamino substituents were used as substrates, and the resulting ratios of ortho- to meta- to para-substituted arene products were measured. No significant electronic effects were observed, indicating that the chemistry is not occurring through a typical electrophilic aromatic substitution pathway. Competition experiments between toluene and other substituted arenes were conducted. Reactivity differences were small, but anisole was found to have the fastest rate of reactio...