The reactions of ground-state boron atoms, B(P-2(j)), with benzene, C6H6(X(1)A(1g)), and deuterated benzene C6D6(X(1)A(1g)), were studied in crossed molecular beam experiments. The reactions were indirect and involved an addition of atomic boron to one carbon atom of benzene following isomerization of the intermediate to the phenylboryl radical, C6H5BH/C6D5BD. The latter decomposed via tight exit transition states by cleavage of the ortho-carbon-hydrogen/deuterium bonds and concomitant ring closures to the aromatic C6H5B/C6D5B isomers, i.e. benzoborirene (p1), plus atomic hydrogen/deuterium. We also detected the (BC6D6)-B-11 adduct. The derived reaction mechanism is also discussed in light of the isoelectronic C7H5+ surface. (c) 2007 Elsevier B.V. All rights reserved.