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首页> 外文期刊>Chemistry: A European journal >Intramolecular C-H/O-H Bond Cleavage with Water and Alcohol Using a Phosphine-Free Ruthenium Carbene NCN Pincer Complex
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Intramolecular C-H/O-H Bond Cleavage with Water and Alcohol Using a Phosphine-Free Ruthenium Carbene NCN Pincer Complex

机译：使用无磷钌碳烯NCN夹杂物用水和酒精进行分子内C-H / O-H键裂解

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摘要

Transition metal complexes that exhibit metal-ligand cooperative reactivity could be suitable candidates for applications in water splitting. Ideally, the ligands around the metal should not contain oxidizable donor atoms, such as phosphines. With this goal in mind, we report new phosphine-free ruthenium NCN pincer complexes with a central N-heterocyclic carbene donor and methylpyridyl N-donors. Reaction with base generates a neutral, dearomatized alkoxo-amido complex, which has been structurally and spectroscopically characterized. The tert-butoxide ligand facilitates regioselective, intramolecular proton transfer through a C-H/O-H bond cleavage process occurring at room temperature. Kinetic and thermodynamic data have been obtained by VT NMR experiments; DFT calculations support the observed behavior. Isolation and structural characterization of a doubly dearomatized phosphine complex also strongly supports our mechanistic proposal. The alkoxo-amido complex reacts with water to form a dearomatized ruthenium hydroxide complex, a first step towards phosphine-free metal-ligand cooperative water splitting.
机译：表现出金属-配体协同反应性的过渡金属络合物可能适合用于水分解。理想地，金属周围的配体不应包含可氧化的供体原子，例如膦。出于这个目标，我们报告了新型的无膦钌NCN钳形配合物，该配合物具有中心N-杂环卡宾供体和甲基吡啶基N-供体。与碱反应生成中性，脱芳基的烷氧基-酰胺基络合物，已在结构和光谱上进行了表征。叔丁氧化物配体通过在室温下发生的C-H / O-H键裂解过程促进区域选择性分子内质子转移。动力学和热力学数据已通过VT NMR实验获得; DFT计算支持观察到的行为。双重脱芳构化的膦复合物的分离和结构表征也强烈支持了我们的机理建议。烷氧基-酰胺基络合物与水反应形成脱芳构的氢氧化钌络合物，这是实现无膦金属-配体协同水分解的第一步。

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