第三族金属单氧化物阳离子负载在 [Fe(CO) ]上的 CO 氧化。
CO Oxidation by Group 3 Metal Monoxide Cations Supported on [Fe(CO) ].
机构信息
School of Chemistry, Biological and Materials Sciences, Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, East China University of Technology, Nanchang, Jiangxi Province, 330013, China.
Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200433, China.
出版信息
Angew Chem Int Ed Engl. 2017 Nov 6;56(45):14096-14101. doi: 10.1002/anie.201707898. Epub 2017 Oct 4.
Infrared photodissociation spectroscopy of mass-selected heteronuclear cluster anions in the form of OMFe(CO) (M=Sc, Y, La) indicates that all these anions involve an 18-electron [Fe(CO) ] building block that is bonded with the M center through two bridged carbonyl ligands. The OLaFe(CO) anion is determined to be a CO-tagged complex involving a [Fe(CO) ] [LaO] anion core. In contrast, the OYFe(CO) anion is characterized to have a [Fe(CO) ] [Y(η -CO )] structure involving a side-on bonded CO ligand. The CO-tagged complex and the [Fe(CO) ] [Sc(η -CO )] isomer co-exist for the OScFe(CO) anion. These observations indicate that both the ScO and YO cations supported on [Fe(CO) ] are able to oxidize CO to CO . Theoretical analyses show that [Fe(CO) ] coordination significantly weakens the MO bond and decreases the energy gap of the interacting valence orbitals between MO and CO, leading to the CO oxidation reactions being both thermodynamically exothermic and kinetically facile.
采用 OMFe(CO)（M=Sc、Y、La）的形式对质量选择的异核团簇负离子进行的红外光解光谱研究表明，所有这些负离子都涉及一个 18 电子的[Fe(CO) ]构建块，该构建块通过两个桥连的羰基配体与 M 中心键合。OLafe(CO) 负离子被确定为一个 CO 标记的配合物，涉及一个[Fe(CO) ] [LaO]负离子核心。相比之下，OYFe(CO) 负离子的特征是具有[Fe(CO) ] [Y(η-CO)]结构，涉及一个侧接的 CO 配体。OScFe(CO) 负离子中存在 CO 标记的配合物和[Fe(CO) ] [Sc(η-CO)]异构体。这些观察结果表明，[Fe(CO) ]上支撑的 ScO 和 YO 阳离子都能够将 CO 氧化为 CO 。理论分析表明，[Fe(CO) ]的配位显著削弱了 MO 键，降低了 MO 和 CO 之间相互作用的价轨道的能隙，导致 CO 氧化反应在热力学上是放热的，动力学上是容易的。
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