Molecular and Electronic Structures of Oxo-bis(benzene-1,2-dithiolato)chromate(V) Monoanions. A Combined Experimental and Density Functional Study

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• 作者：Ruta Kapre ; Kallol Ray ; Isabelle Sylvestre ; Thomas Weyhermü ; ller ; Serena DeBeer George ; Frank Neese ; and Karl Wieghardt
• 刊名：Inorganic Chemistry
• 出版年：2006
• 出版时间：May 1, 2006
• 年：2006
• 卷：45
• 期：9
• 页码：3499 - 3509
• 全文大小：343K
• 年卷期：v.45,no.9(May 1, 2006)
• ISSN：1520-510X

文摘

Two oxo-bis(benzene-1,2-dithiolato)chromate(V) complexes, namely, [CrO(L^Bu)₂]^1- and [CrO(L^Me)₂]^1-, have beensynthesized and studied by UV-vis, EPR, magnetic circular dichroism (MCD), and X-ray absorption spectroscopyand by X-ray crystallography; their electro- and magnetochemistries are reported. H₂L^Bu represents the pro-ligand3,5-di-tert-butylbenzene-1,2-dithiol, and H₂L^Me is the corresponding 4-methyl-benzene-1,2-dithiol. A structural featureof interest for both the complexes is the folding of the dithiolate ligands about the S-S vector providing C_s symmetryto the complexes. Geometry optimizations using all-electron density functional theory with scalar relativistic correctionsat the second-order Douglas-Kroll-Hess (DKH2) and zeroth-order regular approximation (ZORA) levels result inexcellent agreement with the experimentally determined structures and electronic and S K-edge X-ray absorptionspectra. From DFT calculations, the C_s instead of C_2v symmetry for the complexes is attributed to the strong S(3p) Cr(3d_x²-y²) -donation in C_s geometry providing additional stability to the complexes.