磺酰胺三脚架：通过配体修饰调节氧化还原电位
Sulfonamido tripods: tuning redox potentials via ligand modifications.
作者信息
Lau Nathanael, Ziller Joseph W, Borovik A S
机构信息
Department of Chemistry, University of California - Irvine, 1102 Natural Sciences II, Irvine, California 92697-2025, United States.
出版信息
Polyhedron. 2015 Jan 8;85:777-782. doi: 10.1016/j.poly.2014.09.014.
Abstract
A series of Fe-OH complexes were synthesized with ligands based on the tetradentate sulfonamido tripod ,',"-[2,2',2"-nitrilotris(ethane-2,1-diyl)]-tris-({R-Ph}-sulfonamido). These complexes differ by the substituent on the aryl rings and were fully characterized, including their molecular structures via X-ray diffraction methods. All the complexes were five-coordinate with trigonal bipyramidal geometry. A linear correlation was observed between the electronic effects of each ligand, given by the Hammett constants of the -substituents, and the potential of the Fe/Fe redox couple, which were determined using cyclic voltammetry. It was found that the range of redox potentials for the complexes spanned approximately 160 mV.
摘要
基于四齿磺酰胺三脚架配体,'"-[2,2',2"-次氮基三(乙烷-2,1-二基)]-三-({R-苯基}-磺酰胺)合成了一系列铁-氢氧化物配合物。这些配合物因芳环上的取代基不同而有所差异，并通过X射线衍射方法对其进行了全面表征，包括它们的分子结构。所有配合物均为五配位，具有三角双锥几何构型。利用循环伏安法测定了每个配体的电子效应（由-取代基的哈米特常数给出）与Fe/Fe氧化还原电对的电位之间的线性相关性。结果发现，这些配合物的氧化还原电位范围约为160 mV。
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