Six-membered electron transfer series [V(dithiolene)(3)](z) (z = 1+, 0, 1-, 2-, 3-, 4-). An X-ray absorption spectroscopic and density functional theoretical study.
Six-membered electron transfer series [V(dithiolene)(3)](z) (z = 1+, 0, 1-, 2-, 3-, 4-). An X-ray absorption spectroscopic and density functional theoretical study.
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六元电子转移系列[V(二硫烯)(3)](z) (z = 1 , 0, 1-, 2-, 3-, 4-)。
DOI：
10.1021/ic100344f
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发表时间：
2010
影响因子：
4.6
通讯作者：
Wieghardt,Karl
中科院分区：
文献类型：
--
作者：
Sproules,Stephen;Weyhermuller,Thomas;Debeer,Serena;Wieghardt,Karl
利用X射线晶体学、循环伏安法、电子吸收、电子顺磁共振（EPR）和X射线吸收光谱等物理方法，结合密度泛函理论（DFT）计算，对三个二硫杂环戊烯配体配位的钒中心的电子结构进行了研究。从这种方法得到的共有电子结构是V（IV）中心离子，用于该电子转移系列的中性、单阴离子和双阴离子成员，其中三（二硫杂环戊烯）配体单元分别为（L3）4−、（L3）5−·和（L3）6−。三角棱柱单阴离子[VIV（L35−·）]1−（S= 0）被定义为单线态双自由基，其中晶体学上观察到的二硫纶折叠是由金属和配体磁性轨道之间的强反铁磁耦合引起的。这些结果与相应的三（二氧杂环戊烯）钒电子转移系列建立的因素，管理的分子三角棱柱或八面体的几何形状在系统中有三个氧化还原noninnocent配体的对比。
The electronic structures of vanadium centers coordinated by three dithiolene ligands have been elucidated by using a host of physical methods: X-ray crystallography, cyclic voltammetry, electronic absorption, electron paramagnetic resonance (EPR), and X-ray absorption spectroscopies, augmented by density functional theoretical (DFT) calculations. The consensus electronic structure derived from this approach is a V(IV) central ion for the neutral, monoanionic, and dianionic members of this electron transfer series, where the tris(dithiolene) ligand units are (L3)4−, (L3)5−•, and (L3)6−, respectively. The trigonal prismatic monoanions, [VIV(L35−•)]1−(S= 0), are defined as singlet diradicals where the crystallographically observed dithiolene fold results from strong antiferromagnetic coupling between the metal- and ligand-based magnetic orbitals. These results are contrasted with the corresponding tris(dioxolene)vanadium electron transfer series toward establishing the factors that govern the molecular trigonal prismatic or octahedral geometries in systems with three redox noninnocent ligands.