We have studied the addition of reaction between iminoborane HBNH with the B_nN_n cages (n = 12, 16, 28 and 36) for the chemoselectivity (BN bond cleavage and expansion ring vs [2 + 2] cycloaddition) and regioselectivity (square–hexagon junctions vs hexagon–hexagon) of the reaction. Based on our results, the iminoborane molecule can either selectively break a B–N bond of the BN cages, expanding the square ring of the BN cage to a larger one at the surface, or undergo a [2 + 2]-cycloaddition on the BNNT surface. These reactions exhibit a depending on the reactive site of the cages. The square–hexagon B–N bond of the cages prefer bond-cleavage-ring-expansion processes, while hexagon–hexagon B–N bonds follow [2 + 2] cycloaddition reaction. Overall, all reactions are is exothermic while bond-cleavage-ring-expansion processes are a bit more favorable than [2 + 2] cycloadditions with smaller barrier heights. While complexes of iminoborane with hexagon–hexagon bonds at the middle of the larger cages resemble [2 + 2]-cycloaddition, BN bond cleavage also occurred and HBNH acts as a bridge at the top of the decagon. The larger values of HOMO–LUMO gaps for the most stable configurations also indicate kinetically preference the BN bond cleavage and ring expansion processes than the [2 + 2]-cycloaddition reactions.

我们已经研究了亚氨基硼烷HBNH与B _n N _n笼（n = 12、16、28和36）之间的化学选择性（BN键断裂和扩展环与[2 + 2]环加成反应）和区域选择性（方形-六边形连接点与六角形-六边形）。根据我们的结果，亚氨基硼烷分子可以选择性地破坏BN笼的B–N键，将BN笼的方环扩展至表面较大的一个，或在其表面进行[2 + 2]-环加成。 BNNT表面。这些反应表现出取决于笼子的反应位点。笼的正方形-六角形的B–N键更喜欢键断裂环的扩展过程，而六角形–六角形的B–N键遵循[2 + 2]环加成反应。总的来说，所有反应都是放热反应，而键断裂环的扩展过程比具有较小阻隔高度的[2 + 2]环加成反应更有利。亚氨基硼烷在较大笼子中部具有六边形-六边形键的复合物类似于[2 + 2]-环加成反应，但也发生了BN键断裂，HBNH在十边形的顶部充当桥梁。对于最稳定的构型，较大的HOMO–LUMO间隙值也表明，与[2 + 2]-环加成反应相比，BN键的裂解和环扩展过程在动力学上更为偏爱。