College of Pharmacy, Hebei University, Baoding 071002, Hebei People's Republic of China.
Department of Chemistry and Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States.
J Am Chem Soc. 2020 Apr 1;142(13):6244-6250. doi: 10.1021/jacs.0c00409. Epub 2020 Mar 20.
A new molecular system for nitrogen reduction, involving a 2,3'-bipyridine-anchored, end-on-bridging dinitrogen complex of the MeB-BMe intermediate (), has been explored by theoretical methods. The 2,3'-bipyridine-mediated cleavage of the B-B bond in may lead to transient electron-rich sp-hybridized boron species and subsequent activation of the strong N≡N triple bond of the complexed N. Through a boryl transfer sequence, a catalytic cycle may be achieved for the reductive addition of diboranes to a dinitrogen molecule with an energy span of 23 kcal/mol. In addition, the reaction is exothermic by 80.5 kcal/mol, providing a substantive chemical driving force.
理论方法探索了一种新的氮还原分子体系，涉及 MeB-BMe 中间体 () 的 2,3'-联吡啶锚定的、端对桥接的二氮复合物。可能导致瞬态富电子 sp 杂化硼物种的形成，并随后激活复合物中 N≡N 三重键的活性。通过硼基转移序列，可以实现二硼烷对氮气分子的还原加成的催化循环，能量跨度为 23 kcal/mol。此外，反应放热 80.5 kcal/mol，提供了实质性的化学驱动力。
