Kapre Ruta, Ray Kallol, Sylvestre Isabelle, Weyhermüller Thomas, DeBeer George Serena, Neese Frank, Wieghardt Karl
Max-Planck Institut für Bioanorganische Chemie, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany.
Inorg Chem. 2006 May 1;45(9):3499-509. doi: 10.1021/ic051844s.
Two oxo-bis(benzene-1,2-dithiolato)chromate(V) complexes, namely, [CrO(L(Bu))2]1- and [CrO(L(Me))2]1-, have been synthesized and studied by UV-vis, EPR, magnetic circular dichroism (MCD), and X-ray absorption spectroscopy and by X-ray crystallography; their electro- and magnetochemistries are reported. H2L(Bu) represents the pro-ligand 3,5-di-tert-butylbenzene-1,2-dithiol, and H2L(Me) is the corresponding 4-methyl-benzene-1,2-dithiol. A structural feature of interest for both the complexes is the folding of the dithiolate ligands about the S-S vector providing Cs symmetry to the complexes. Geometry optimizations using all-electron density functional theory with scalar relativistic corrections at the second-order Douglas-Kroll-Hess (DKH2) and zeroth-order regular approximation (ZORA) levels result in excellent agreement with the experimentally determined structures and electronic and S K-edge X-ray absorption spectra. From DFT calculations, the Cs instead of C2v symmetry for the complexes is attributed to the strong S(3p) --> Cr(3d(x2-y2)) pi-donation in Cs geometry providing additional stability to the complexes.
已合成了两种氧代双（苯 - 1,2 - 二硫醇根）铬（V）配合物，即[CrO(L(Bu))2]1-和[CrO(L(Me))2]1-，并通过紫外可见光谱、电子顺磁共振、磁圆二色性（MCD）、X射线吸收光谱以及X射线晶体学对其进行了研究；报道了它们的电化学和磁化学性质。H2L(Bu)代表前体配体3,5 - 二叔丁基苯 - 1,2 - 二硫醇，H2L(Me)是相应的4 - 甲基苯 - 1,2 - 二硫醇。这两种配合物的一个有趣结构特征是二硫醇盐配体围绕S - S向量折叠，使配合物具有Cs对称性。使用全电子密度泛函理论并在二阶道格拉斯 - 克罗尔 - 赫斯（DKH2）和零阶正则近似（ZORA）水平进行标量相对论校正的几何优化，与实验测定的结构以及电子和S K边X射线吸收光谱结果非常吻合。通过密度泛函理论计算，配合物具有Cs而非C2v对称性归因于在Cs几何构型中强烈的S(3p)→Cr(3d(x2 - y2)) π - 给予作用，为配合物提供了额外的稳定性。
