Electronic Structure of Thiolate-bridged Diiron Complexes and a Single-electron Oxidation Reaction＂ A Combination of Experimental and Computational Studies  

作　　者：Si Chen Lun Luo Yang Li Dawei Yang Jingping Qu Yi Luo 

机构地区：[1]State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian, Liaoning 116024, China

出　　处：《Chinese Journal of Chemistry》2016年第9期919-924,共6页中国化学（英文版）

基　　金：This work was partly supported by the National Natural Science Foundation of China （Nos. 21429201, 21231003, 21571026）. The authors also thank the Network and Information Center of the Dalian University of Technology for part of the computational resources.

摘　　要：Single-electron oxidation of a diiron-sulfur complex [Cpπ＊Fe（μ-bdt）FeCp^＊] （1, Cp^＊=η^5-C5Me5; bdt = benzene-1,2-dithiolate） to [Cp^＊Fe（μ-bdt）FeCp^＊]]^＋ （2） has been experimentally conducted. The bdt ligand with redoxactive character has been computationally proposed to be a dianion （bdt62-） rather than previously proposed monoanion （bdt^-） radical in 1 though it has un-equidistant aromatic C-C bond lengths. The ground state of 1 is predicted to be two low-spin ferrous ions （SFe= 0） and 2 has a medium-spin ferric ion （SFe= 1/2） and a low-spin ferrous center （SFe=0）, and the oxidation of 1 to 2 is calculated to be a single-metal-based process. Both complexes have no significant antiferromagnetic coupling character.Single-electron oxidation of a diiron-sulfur complex [Cpπ＊Fe（μ-bdt）FeCp^＊] （1, Cp^＊=η^5-C5Me5; bdt = benzene-1,2-dithiolate） to [Cp^＊Fe（μ-bdt）FeCp^＊]]^＋ （2） has been experimentally conducted. The bdt ligand with redoxactive character has been computationally proposed to be a dianion （bdt62-） rather than previously proposed monoanion （bdt^-） radical in 1 though it has un-equidistant aromatic C-C bond lengths. The ground state of 1 is predicted to be two low-spin ferrous ions （SFe= 0） and 2 has a medium-spin ferric ion （SFe= 1/2） and a low-spin ferrous center （SFe=0）, and the oxidation of 1 to 2 is calculated to be a single-metal-based process. Both complexes have no significant antiferromagnetic coupling character.

关 键 词：density functional theory iron-sulfur cluster benzene-1 2-dithiolate non-innocent ligand single-electron oxidation 

分 类 号：O[理学]