Miller Glenn B S, Uggerud Einar
Mass Spectrometry Laboratory and Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, University of Oslo, PO Box 1033 Blindern, 0135, Oslo, Norway.
Chemistry. 2018 Mar 26;24(18):4710-4717. doi: 10.1002/chem.201706069. Epub 2018 Feb 27.
Gas-phase activation of CO by chloride tagged metal atoms, [ClM] (M=Mg, Zn), has been investigated by mass spectrometry and high-level quantum chemistry. Both metals activate CO with significant bending of the CO moiety to form complexes with the general formula [ClM,CO ] . The structure of the metal-CO complex depends on the method of formation, and the energy landscapes and reaction dynamics have been probed by collisional induced dissociation and thermal ion molecule reactions with isotopically labeled species. Having established these structural relationships, the gas-phase reactivity of [ClM(κ -O C)] with acetaldehyde (here considered a carbohydrate mimic) was then studied. Formation of lactate and enolate-pyruvate complexes are observed, showing that CO fixation by C-C bond formation takes place. For M=Zn, even formation of free pyruvate ([C H O ] ) is observed. Implications of the observed CO reactivity for the electrochemical conversion of carbon dioxide, and to biochemical and artificial photosynthesis is briefly discussed. Detailed potential energy diagrams obtained by the quantum chemical calculations offer models consistent with experimental observation.
通过质谱法和高水平量子化学研究了氯化物标记的金属原子[ClM]（M = Mg，Zn）对CO的气相活化。两种金属均通过CO部分的显著弯曲来活化CO，以形成通式为[ClM,CO]的配合物。金属-CO配合物的结构取决于形成方法，并且通过碰撞诱导解离以及与同位素标记物种的热离子分子反应来探测能量景观和反应动力学。在建立了这些结构关系之后，接着研究了[ClM(κ -O C)]与乙醛（在此被视为碳水化合物模拟物）的气相反应活性。观察到了乳酸盐和烯醇盐-丙酮酸盐配合物的形成，表明通过碳-碳键形成实现了CO固定。对于M = Zn，甚至观察到了游离丙酮酸盐（[C₃H₃O₃⁻]）的形成。简要讨论了所观察到的CO反应活性对二氧化碳电化学转化以及对生化和人工光合作用的意义。通过量子化学计算获得的详细势能图提供了与实验观察结果一致的模型。
