J Am Chem Soc. 2019 Aug 21;141(33):12962-12966. doi: 10.1021/jacs.9b05591. Epub 2019 Aug 7.
We report the hydrogenation of carbamates and urea derivatives, two of the most challenging carbonyl compounds to be hydrogenated, catalyzed for the first time by a complex of an earth-abundant metal. The hydrogenation reaction of these CO-derived compounds, catalyzed by a manganese pincer complex, yields methanol in addition to amine and alcohol, which makes this methodology a sustainable alternative route for the conversion of CO to methanol, involving a base-metal catalyst. Moreover, the hydrogenation proceeds under mild pressure (20 bar). Our observations support a hydrogenation mechanism involving the Mn-H complex. A plausible catalytic cycle is proposed based on informative mechanistic experiments.
我们首次报道了由一种丰富的地球金属配合物催化的氨基甲酸酯和脲衍生物的氢化反应，这两种化合物是最难氢化的羰基化合物之一。在锰钳形配合物的催化作用下，这些 CO 衍生化合物的加氢反应除了生成胺和醇外，还生成甲醇，这使得该方法成为将 CO 转化为甲醇的一种可持续的替代途径，涉及到一种基础金属催化剂。此外，该氢化反应在温和的压力（20 巴）下进行。我们的观察结果支持涉及 Mn-H 配合物的氢化机理。根据有启发性的机理实验，提出了一个合理的催化循环。
