Exploration of the Solid- and Solution-State Structures and Electrochemical Properties of Ce IV (atrane) Complexes
Exploration of the Solid- and Solution-State Structures and Electrochemical Properties of Ce IV (atrane) Complexes
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Ce IV（阿特拉烷）配合物的固态和溶液态结构及电化学性质的探索
DOI：
10.1021/acs.inorgchem.8b00712
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发表时间：
2018
影响因子：
4.6
通讯作者：
Schelter, Eric J.
中科院分区：
文献类型：
--
作者：
Solola, Lukman A.;Cheisson, Thibault;Yang, Qiaomu;Carroll, Patrick J.;Schelter, Eric J.
铈络合物的化学氧化可能是不可预测的，因为不稳定的金属-配体键导致配体重新分布。使用三脚架框架，如甲硅烷基取代的tren配体（NN′3= [N（CH 2CH 2N（SiMe 2 tBu））3]3-）和三（羟基氨基）配体[（（2-tBuNO）C6 H4 CH 2）3 N]3-（TriNOx 3-），已经显示出减轻配体再分布效应，以允许获得具有不同顶端配体的四价铈络合物。本文研究了CeIV与三脚架atrane 3-（H3 atrane = [N（CH 2C（CH 3）2 OH）3]）配体的配位化学。合成了一系列CeIV（atrane）配合物，并通过X-射线衍射对其结构进行了表征。利用1H和扩散有序（DOSY）NMR谱研究了这些配合物的溶液态行为。研究了氮杂三环骨架内CeIV阳离子的电化学稳定性。我们的研究结果表明，合适的顶端配体和atrane框架的组合提供了优异的稳定CeIV阳离子。
Chemical oxidation of cerium complexes can be unpredictable because of labile metal–ligand bonds leading to ligand redistribution. The use of tripodal frameworks such as silyl-substituted tren ligands (NN′3= [N(CH2CH2N(SiMe2tBu))3]3–) and a tris(hydroxylaminato) ligand, [((2-tBuNO)C6H4CH2)3N]3–(TriNOx3–), has been shown to mitigate ligand redistribution effects to allow access to tetravalent cerium complexes with different apical ligands. In the current work, the coordination chemistry of CeIVwith the related tripodal atrane3–(H3atrane = [N(CH2C(CH3)2OH)3]) ligand framework was examined. A series of CeIV(atrane) complexes with supporting chloride, silylamide, and aryloxide ligands were synthesized and characterized by X-ray crystallography. The solution-state behaviors of these complexes were studied using1H and diffusion-ordered (DOSY) NMR spectroscopies. The electrochemical stabilization of the CeIVcation within the atrane3–framework was examined. Our results showed that a combination of suitable apical ligands and the atrane framework provided excellent stabilization for the CeIVcation.