Department of Chemistry, National Taiwan University, Taipei 106, Taiwan.
J Comput Chem. 2010 Sep;31(12):2258-62. doi: 10.1002/jcc.21515.
According to our theoretical approaches, a cyclic boryl anion can act as a Lewis base like its isoelectronic counterpart N-heterocyclic carbene, reducing the homolytic bond dissociation energy of B-H in BH(3). However, the donating efficiency is affected by the counter cation in both gas phase and nonpolar solvents. Moreover, we also predict the seven-membered ring boryl anion 5, although it has not yet synthesized, to be the most efficient reagent to reduce the bond dissociation energy of a B-H bond in BH(3). This study may thus pave another avenue toward Lewis base induced hydrogen atom abstraction in BH(3).
根据我们的理论方法，环状硼阴离子可以像其等电子体 N-杂环卡宾一样充当路易斯碱，降低 BH(3)中 B-H 的均裂键离解能。然而，在气相和非极性溶剂中，供电子效率都受到抗衡阳离子的影响。此外，我们还预测尚未合成的七元环硼阴离子 5 是还原 BH(3)中 B-H 键离解能的最有效试剂。因此，这项研究为路易斯碱诱导 BH(3)中的氢原子提取开辟了另一条途径。
