A trans-1,2 End-On Disulfide-Bridged Iron鈥揟etracarbene Dimer and Its Electronic Structure

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• 作者：Steffen Meyer ; Oliver Krahe ; Claudia Kupper ; Iris Klawitter ; Serhiy Demeshko ; Eckhard Bill ; Frank Neese ; Franc Meyer
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：October 19, 2015
• 年：2015
• 卷：54
• 期：20
• 页码：9770-9776
• 全文大小：419K
• ISSN：1520-510X

文摘

A disulfide-bridged diiron complex with [Fe鈥揝鈥揝鈥揊e] core, which represents an isomer of the common biological [2Fe鈥?S] ferredoxin-type clusters, was synthesized using strongly 蟽-donating macrocyclic tetracarbene capping ligands. Though the complex is quite labile in solution, single crystals were obtained, and the structure was elucidated by X-ray diffraction. The electron-rich iron鈥搒ulfur core is found to show rather unusual magnetic and electronic properties. Experimental data and density functional theory studies indicate extremely strong antiferromagnetic coupling (鈭?i>J > 800 cm^鈥?) between two low-spin iron(III) ions via the S₂^{2鈥?/sup> bridge, and the intense near-IR absorption characteristic for the [Fe鈥揝鈥揝鈥揊e] core was assigned to a S 鈫?Fe ligand-to-metal charge transfer transition.}