Simple transition-metal complexes of the formula Cp*M(CO)(n)BR2 [Cp* = C-5(CH3)(5)] containing an electrophilic, covalently bound main-group ligand react with alkanes and release products resulting from selective functionalization of an alkane at the terminal position. These reactions produce alkylboronate esters, which are common reagents in organic synthesis, Thus, the boryl complexes are rare chemical reagents that react selectivity at the terminal position of an alkane to provide simple functionalized products. Mechanistic analysis shows that ligand dissociation is induced photochemically and that thermal reaction of the resulting intermediate occurs with alkanes.