The mechanisms of the reactions of a boron atom (P-2) and of B-2 ((3)Sigma(g)(-)) With ammonia were studied computationally at the hybrid DFT B3LYP/6-311++G(3df, 2p)//B3LYP/6-311++G(2d,p) level. The B and B-2 insertions into NH bonds take place by initial formation of BN and BBNH3 complexes. As found previously for methane and water, B-2 also is more-reactive than B with ammonia. The energy-rich boron atom insertion product, HBNH2, then gives the species HBNH2, H2BNH, HBNH, and BNH. These can react with a second boron atom to give novel boron-containing compounds such as HBNBH, BNBH, H2BNBH, and BNB, some of which have been observed experimentally. However, contrary to the experimental suppositions, the only cyclic B2N minimum was a high-energy species.