Highly Active Ruthenium CNC Pincer Photocatalysts for Visible-Light-Driven Carbon Dioxide Reduction
Highly Active Ruthenium CNC Pincer Photocatalysts for Visible-Light-Driven Carbon Dioxide Reduction
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DOI：
10.1021/acs.inorgchem.9b00791
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发表时间：
2019-06-17
影响因子：
4.6
通讯作者：
Papish, Elizabeth T.
中科院分区：
文献类型：
--
作者：
Das, Sanjit;Rodrigues, Roberta R.;Papish, Elizabeth T.
本文所述的五种钌催化剂促进自敏化二氧化碳还原以形成具有钌催化中心的一氧化碳。这些催化剂包括四个新的和一个以前报道的CNC钳配合物，其特征在于吡啶醇衍生的N供体和N-杂环卡宾（NHC）衍生自咪唑或苯并咪唑的C-供体。配合物的特点是充分的光谱和分析方法，包括X射线晶体学。在NHC配体上引入2，2 '-联吡啶（bipy）共配体和苯基对于快速催化是必要的。[（CNC）Ru（bipy）（CH 3CN）]（OTf）（2）是文献中用于CO2还原而无需外部光敏剂的最活性和最耐用的光催化剂之一。该配合物的结构在催化中的作用进行了讨论，包括钳的苯基翼尖，联吡啶配体，和弱协调单齿配体的重要性。
Five ruthenium catalysts described herein facilitate self-sensitized carbon dioxide reduction to form carbon monoxide with a ruthenium catalytic center. These catalysts include four new and one previously reported CNC pincer complexes featuring a pyridinol derived Ndonor and N-heterocyclic carbene (NHC) C-donors derived from imidazole or benzimidazole. The complexes have been characterized fully by spectroscopic and analytic methods, including X-ray crystallography. Introduction of a 2,2'-bipyridine (bipy) coligand and phenyl groups on the NHC ligand was necessary for rapid catalysis. [(CNC)Ru(bipy)(CH3CN)](OTf)(2) is among the most active and durable photocatalysts in the literature for CO2 reduction without an external photosensitizer. The role of the structure of this complex in catalysis is discussed, including the importance of the pincer's phenyl wingtips, the bipyridyl ligand, and a weakly coordinating monodentate ligand.