Ma Howard Z, Canty Allan J, O'Hair Richard A J
School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, University of Melbourne, 30 Flemington Rd, Parkville, Victoria 3010, Australia.
School of Natural Sciences - Chemistry, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia.
Dalton Trans. 2023 Feb 7;52(6):1574-1581. doi: 10.1039/d2dt03764e.
A near thermal two-step catalytic cycle for the selective release of hydrogen from formic acid by mononuclear cuprate anions was revealed using multistage mass spectrometry experiments, deuterium labelling and DFT calculations. In gas-phase ion-molecule reactions, mononuclear copper hydride anions [(L)Cu(H)] (where L = H, OCH, BH and CN) were found to react with formic acid (HCOH) to yield [(L)Cu(OCH)] and H. The copper formate anions [(L)Cu(OCH)] can decarboxylate collision-induced dissociation (CID) to reform the copper hydride [(L)Cu(H)], thereby closing the two-step catalytic cycle. Analogous labelling experiments with -formic acid (DCOH) reveal that the decarboxylation process also occurs spontaneously. A kinetic study was carried out to provide further insights into the species involved in this reaction. Energetics from density functional theory (DFT) calculations show that the key decarboxylation step can occur without CID, thus in support of experimental observations.
通过多级质谱实验、氘标记和密度泛函理论（DFT）计算，揭示了一种近热两步催化循环，用于单核铜酸盐阴离子从甲酸中选择性释放氢气。在气相离子 - 分子反应中，发现单核氢化铜阴离子[（L）Cu（H）]（其中L = H、OCH、BH和CN）与甲酸（HCOH）反应生成[（L）Cu（OCH）]和H。甲酸铜阴离子[（L）Cu（OCH）]可通过碰撞诱导解离（CID）脱羧，重新形成氢化铜[（L）Cu（H）]，从而完成两步催化循环。用 - 甲酸（DCOH）进行的类似标记实验表明，脱羧过程也能自发发生。进行了动力学研究，以进一步深入了解该反应中涉及的物种。密度泛函理论（DFT）计算得出的能量学结果表明，关键的脱羧步骤无需CID即可发生，从而支持了实验观察结果。
