Design, Identification, and Evolution of a Surface Ruthenium(II/III) Single Site for CO Activation.
Design, Identification, and Evolution of a Surface Ruthenium(II/III) Single Site for CO Activation.
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DOI：
10.1002/anie.202008370
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发表时间：
2021-01-18
期刊：
影响因子：
--
通讯作者：
Wang FR
中科院分区：
文献类型：
--
作者：
Kang L;Wang B;Thetford A;Wu K;Danaie M;He Q;Gibson EK;Sun LD;Asakura H;Catlow CRA;Wang FR
RuII化合物广泛用于催化、催化剂和医学应用。它们通常在还原环境中获得，因为分子O2可以将RuII氧化为RuIII和RuIV。在这里，我们报告的设计，鉴定和演变的空气稳定的表面[bipy-RuII（CO）2Cl 2]网站是共价安装到聚亚苯基框架。这样的RuII位点是通过[bipy-RuIIICl 4]−的还原和同时从Cl−到CO的配体交换获得的。这种结构演变通过原位X射线和红外光谱研究的结合来证明。 [bipy-RuII（CO）2Cl 2]位在462 K时可以氧化CO，转换频率为0.73×10−2 s−1，而RuIII位则完全不活泼。 这项工作有助于研究的结构与活性的关系，通过展示一个实际的控制在分子水平上的几何和电子结构的单中心催化剂。空气稳定的表面[bipy-RuII（CO）2Cl 2]单位点被设计用于CO氧化，而所有其他RuIII单位点都没有活性。该方法进一步扩展到9个过渡金属单中心系统，使表面配位化学在多相催化中的应用成为可能。
RuII compounds are widely used in catalysis, photocatalysis, and medical applications. They are usually obtained in a reductive environment as molecular O2 can oxidize RuII to RuIII and RuIV. Here we report the design, identification and evolution of an air‐stable surface [bipy‐RuII(CO)2Cl2] site that is covalently mounted onto a polyphenylene framework. Such a RuII site was obtained by reduction of [bipy‐RuIIICl4]− with simultaneous ligand exchange from Cl− to CO. This structural evolution was witnessed by a combination of in situ X‐ray and infrared spectroscopy studies. The [bipy‐RuII(CO)2Cl2] site enables oxidation of CO with a turnover frequency of 0.73×10−2 s−1 at 462 K, while the RuIII site is completely inert. This work contributes to the study of structure–activity relationship by demonstrating a practical control over both geometric and electronic structures of single‐site catalysts at molecular level. An air‐stable surface [bipy‐RuII(CO)2Cl2] single site is designed towards CO oxidation, while all other RuIII single sites are not active. The methodology is further extended to nine transition‐metal single‐site systems, enabling the use of surface coordination chemistry in heterogeneous catalysis.
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