Oxygen Evolution Catalysed by a Mononuclear Ruthenium Complex bearing Pendant -SO3– Groups
Oxygen Evolution Catalysed by a Mononuclear Ruthenium Complex bearing Pendant -SO3– Groups
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单核钌配合物-SO3-基团催化析氧
DOI：
10.1002/anie.201503365
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
Shigeyuki Masaoka
中科院分区：
文献类型：
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作者：
Masaki Yoshida;Mio Kondo;Sena Torii;Ken Sakai;Shigeyuki Masaoka
能够顺利形成OO键的催化体系的合理分子设计对于开发高效的水氧化催化剂至关重要。开发了一种新的钌配合物，其在二级配位层中带有SO3−基团：[Ru(terpy)(bpyms)(OH2)]（terpy=2,2′:6′,2′′-三联吡啶，bpyms=2,2′-联吡啶-5,5′-双（甲磺酸盐））。与母体催化剂[Ru(terpy)(bpy)(OH2)]2+(bpy=2,2′-联吡啶)相比，引入SO3−基团后，Ce4+氧化剂驱动的水氧化明显加速。光谱、电化学和晶体学研究得出结论，SO3−基团通过催化剂上的二次配位球促进OO键的形成，而SO3−基团对[Ru(terpy)(bpy)(OH2)]2+核的电子结构的影响可以忽略不计。这项工作的结果表明，二次配位层的修饰对于水氧化催化剂的设计是一种有价值的策略。
Rational molecular design of catalytic systems capable of smooth OO bond formation is critical to the development of efficient catalysts for water oxidation. A new ruthenium complex was developed, which bears pendant SO3−groups in the secondary coordination sphere: [Ru(terpy)(bpyms)(OH2)] (terpy=2,2′:6′,2′′‐terpyridine, bpyms=2,2′‐bipyridine‐5,5′‐bis(methanesulfonate)). Water oxidation driven by a Ce4+oxidant is distinctly accelerated upon introduction of the pendant SO3−groups in comparisons to the parent catalyst, [Ru(terpy)(bpy)(OH2)]2+(bpy=2,2′‐bipyridine). Spectroscopic, electrochemical, and crystallographic investigations concluded that the pendant SO3−groups promote the formation of an OO bond via the secondary coordination sphere on the catalyst, whereas the influence of the pendant SO3−groups on the electronic structure of the [Ru(terpy)(bpy)(OH2)]2+core is negligible. The results of this work indicate that modification of the secondary coordination sphere is a valuable strategy for the design of water oxidation catalysts.