Novel theoretical studies of the dehydrogenation of LiBH 2 NH 3

It is believed that the dehydrogenation of LiNH 2 BH 3 (LAB) proceeds through a combination of the decomposition of the LiBH 2 NH 3 (LBA) and LAB isomers. The dehydrogenation of LBA, an isomer of LAB, is discussed in this article. It is demonstrated that the loss of H 2 from LBA takes place in a two‐step reaction. Studies of the dehydrogenation process were performed using Møller–Plesset second‐order perturbation theory with a 6‐311++G(3df,2pd) basis set. The intrinsic reaction coordinate was calculated to determine the minimum energy paths. Finally, the rate constants were obtained using the transition‐state theory (TST), TST/Eckart, canonical variational transition‐state theory (CVT), CVT/small‐curvature tunneling correction, and CVT/zero‐curvature tunneling correction methods from 200 to 2500 K. This is the first report on a different dehydrogenation mechanism for an alkali‐metal amidoborane, and the energy barrier of LBA is much lower than that of the traditionally studied LAB. © 2012 Wiley Periodicals, Inc.