Photoirradiation of a solution of BH3 center dot NHR2 (1a: R = Me, 1b: R = 1/2C(4)H(8), 1c: R = 1/2C(5)H(10) 1f: R = Et) containing a catalytic amount of a group-6 metal carbonyl complex. [M(CO)(6)] (M = Cr, Mo, W), led to dehydrogenative B- N covalent bond formation to produce aminoborane dinners, [BH2NR2](2) (2a-c, f), in high yield. During these reactions a borane a complex, [M(CO)(5)(eta(1)-BH3 center dot NHR2)] (3), was detected by NMR spectroscopy. Similar catalytic dehydrogenation of bulkier amineboranes, BH3 center dot NH'Pr-2 (1d) and BH3 center dot NHCy2 (1e, Cy = cyclo-C5H11), afforded monomeric products BH2=NR2 (4d, e) The reaction mechanism of the clehydrocoupling was investigated by DFT calculations. On the basis of the computational study, we propose that the catalytic dehydrogenation reactions proceed via an intramolecular pathway and that the active catalyst is [Cr(CO)(4)] The reaction follows a stepwise mechanism involving NH and BH activation. Dehydrocoupling of borane-primary amine adducts BH3 center dot NH2R (1g: R = Me, 1h: R = Et, 1i: R = Bu) gave borazine derivatives [BHNR](3) (59-i).