Proton Induced Generation of rNHC Ru Complex
Proton Induced Generation of rNHC Ru Complex
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质子诱导生成 rNHC Ru 复合物
DOI：
10.1002/chem.201404932
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发表时间：
2015
期刊：
影响因子：
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通讯作者：
M. Ehara
中科院分区：
文献类型：
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作者：
T. Fukushima;R. Fukuda;K. Kobayashi;G.F. Caramori;G. Frenking;M. Ehara
之前发现质子诱导的 RuC 键变化与水氧化有关，现已通过使用具有三种菲咯啉 (phen) 异构体的环金属化钌配合物进行了研究。新合成了设计的配合物[Ru(bpy)2(1,5-phen)]+([2]+)、[Ru(bpy)2(1,6-phen)]+([3]+)和[Ru(bpy)2(1,7-phen)]+([4]+)，并通过各种光谱和理论方案分析了它们的结构和电子性质。 [4]+的质子化引发了深刻的电子结构变化，形成远程N-杂环卡宾（rNHC），而[2]+和[3]+的质子化不影响它们的结构。研究发现，phen 电子结构超出经典共振形式的变化控制着 rNHC 行为。本研究为相关钌催化剂的配体设计提供了新的见解。
The proton‐induced RuC bond variation, which was previously found to be relevant in the water oxidation, has been investigated by using cyclometalated ruthenium complexes with three phenanthroline (phen) isomers. The designed complexes, [Ru(bpy)2(1,5‐phen)]+([2]+), [Ru(bpy)2(1,6‐phen)]+([3]+), and [Ru(bpy)2(1,7‐phen)]+([4]+) were newly synthesized and their structural and electronic properties were analyzed by various spectroscopy and theoretical protocols. Protonation of [4]+triggered profound electronic structural change to form remote N‐heterocyclic carbene (rNHC), whereas protonation of [2]+and [3]+did not affect their structures. It was found that changes in the electronic structure of phen beyond classical resonance forms control the rNHC behavior. The present study provides new insights into the ligand design of related ruthenium catalysts.