Qu Zheng-Wang, Zhu Hui, Streubel Rainer, Grimme Stefan
Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4, 53115 Bonn, Germany.
Institut für Anorganische Chemie, University of Bonn, Gerhard-Domagk Straße 1, D-53121 Bonn, Germany.
Phys Chem Chem Phys. 2022 Jun 15;24(23):14159-14164. doi: 10.1039/d2cp00590e.
Extensive DFT calculations show that BHNH may transfer dihydrogen as separated hydride and proton to CO rather than HCO in water over a barrier of 25.9 kcal mol, followed by faster hydride transfer from borate anions to either electrophilic CO or protic HO or HCOH, leading to competitive formate production and H release.
广泛的密度泛函理论（DFT）计算表明，在水中，BHNH可能会以分离的氢化物和质子的形式将二氢转移给CO而非HCO，其势垒为25.9千卡/摩尔，随后硼酸盐阴离子会更快地将氢化物转移给亲电的CO或质子性的HO或HCOH，从而导致竞争性地生成甲酸盐并释放出H。
