Electronic Structure of the [Tris(dithiolene)chromium]z(z=0, 1-, 2-, 3-) Electron Transfer Series and Their Manganese(IV) Analogues. An X-ray Absorption Spectroscopic and Density Functional Theoretical Study

被引：80

作者：

Banerjee, Priyabrata ^{[1
]}

Sproules, Stephen ^{[1
]}

Weyhermueller, Thomas ^{[1
]}

George, Serena DeBeer ^{[2
]}

Wieghardt, Karl ^{[1
]}

机构：

[1] Max Planck Inst Bioanorgan Chem, D-45470 Mulheim, Germany

[2] Stanford Univ, SLAC, Stanford Synchrotron Radiat Lightsource, Stanford, CA 94309 USA

来源：

INORGANIC CHEMISTRY | 2009年 / 48卷 / 13期

关键词：

TRANSITION-METAL-COMPLEXES; TRIGONAL-PRISMATIC COORDINATION; IRON TRANSPORT COMPOUNDS; GAUSSIAN-BASIS SETS; MOLECULAR-STRUCTURE; CORRELATION-ENERGY; CRYSTAL-STRUCTURE; ATOMS LI; SEMIQUINONE; APPROXIMATION;

D O I：

10.1021/ic900154v

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Three members of the electron transfer series [Cr-III(dithiolene)(3)](z) (z = 1-, 2-, 3-) along with [Mn-IV(dithiolene)(3)](2-) analogues are shown to possess Cr(III) and Mn(IV) ions, respectively, by X-ray absorption spectroscopy (Cr and Mn K-edges). S K-edge spectra show the Cr series to be linked by ligand-based redox processes. All complexes are octahedral with DFT calculations reproducing the molecular structures and spectroscopic parameters such that [Cr(dithiolene)(3)](0) is predicted to be and octahedral with three S,S'-coordinated radical ligands.

引用

页码：5829 / 5847

页数：19

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