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具有氧化还原活性三(二茂铁基)三嗪主链的三配位硬币金属配合物具有三嗪-金属相互作用。

Tricoordinate Coinage Metal Complexes with a Redox-Active Tris-(Ferrocenyl)triazine Backbone Feature Triazine-Metal Interactions.

作者信息

Straube Axel, Coburger Peter, Ringenberg Mark R, Hey-Hawkins Evamarie

机构信息

Institute of Inorganic Chemistry, Universität Leipzig, Johannisallee 29, 04103, Leipzig, Germany.

Present address: Institute of Inorganic Chemistry, Universität Regensburg, Universitätsstraße 31, 93051, Regensburg, Germany.

出版信息

Chemistry. 2020 May 7;26(26):5758-5764. doi: 10.1002/chem.202000226. Epub 2020 Apr 22.

Abstract

2,4,6-Tris(1-diphenylphosphanyl-1'-ferrocenylene)-1,3,5-triazine (1) coordinates all three coinage metal(I) ions in a 1:1 tridentate coordination mode. The C -symmetric coordination in both solid state and solution is stabilised by an uncommon cation-π interaction between the triazine core and the metal cation. Intramolecular dynamic behaviour was observed by variable-temperature NMR spectroscopy. The borane adduct of 1, 1BH , displays four accessible oxidation states, suggesting complexes of 1 to be intriguing candidates for redox-switchable catalysis. Complexes 1Cu, 1Ag, and 1Au display a more complicated electrochemical behaviour, and the electrochemical mechanism was studied by temperature-resolved UV/Vis spectroelectrochemistry and chemical oxidation.

摘要

2,4,6-三(1-二苯基膦基-1'-二茂铁撑基)-1,3,5-三嗪(1)以1:1的三齿配位模式与所有三种第一族金属离子配位。三嗪核心与金属阳离子之间罕见的阳离子-π相互作用使固态和溶液中的C对称配位得以稳定。通过变温核磁共振光谱观察到分子内动态行为。1的硼烷加合物1BH显示出四种可及氧化态,这表明1的配合物是氧化还原可切换催化的有趣候选物。配合物1Cu、1Ag和1Au表现出更复杂的电化学行为,并通过温度分辨紫外/可见光谱电化学和化学氧化研究了其电化学机理。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ba3b/7317378/f00043ab2c66/CHEM-26-5758-g001.jpg

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