Electroreduction of Benzaldehyde with a Metal-Ligand Bifunctional Hydroxycyclopentadienyl Molybdenum(II) Hydride
Electroreduction of Benzaldehyde with a Metal-Ligand Bifunctional Hydroxycyclopentadienyl Molybdenum(II) Hydride
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DOI：
10.1021/acs.organomet.0c00630
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发表时间：
2020-12-18
期刊：
影响因子：
2.8
通讯作者：
Waymouth, Robert M.
中科院分区：
文献类型：
--
作者：
Armstrong, Keith C.;Waymouth, Robert M.
本文介绍了一种电催化苯甲醛加氢制苯甲醇和二苄醚的体系。氢化钼（C_5Ph_4OH）Mo（CO）（3）（H）（3）被证明是活跃的氢化物种。这种氢化物被证明是显着的酸稳定，导致约。尽管在强酸性和还原性条件下，醛还原的法拉第效率仍高于氢释放的法拉第效率67%。氢化物3通过阳离子[（C5 Ph 4 OH）Mo（CO）（3）（CH 3CN）][OTf]（[2][OTf]）的1-质子-2-电子还原来制备，阳离子[（C5 Ph 4 O）Mo（CO）（3）（L）]（1）通过Mo（0）前体[（C5 Ph 4 O）Mo（CO）（3）（L）]（1）的质子化产生。
An electrocatalytic system for the hydrogenation of benzaldehyde to benzyl alcohol and dibenzyl ether is described. The molybdenum hydride (C5Ph4OH)Mo(CO)(3)(H) (3) is shown to be the actively hydrogenating species. This hydride is demonstrated to be remarkably acid-stable, leading to a ca. 67% Faradaic efficiency for aldehyde reduction over hydrogen evolution despite strongly acidic and reducing conditions. Hydride 3 is prepared via 1-proton-2-electron reduction of cation [(C5Ph4OH)Mo(CO)(3)(CH3CN)][OTf] ([2][OTf]), which is generated by protonation of the Mo(0) precursor [(C5Ph4O)Mo(CO)(3)(L)](1).