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论文类型：期刊论文

发表时间：2016-09-01

发表刊物：CHINESE JOURNAL OF CHEMISTRY

收录刊物：SCIE、Scopus

卷号：34

期号：9

页面范围：919-924

ISSN号：1001-604X

关键字：density functional theory; iron-sulfur cluster; benzene-1,2-dithiolate; non-innocent ligand; single-electron oxidation

摘要：Single-electron oxidation of a diiron-sulfur complex [Cp*Fe(mu-bdt)FeCp*] (1, Cp* = eta(5)-C5Me5; bdt = benzene-1,2-dithiolate) to [Cp*Fe(mu-bdt)FeCp*](+) (2) has been experimentally conducted. The bdt ligand with redox-active character has been computationally proposed to be a dianion (bdt(2-)) rather than previously proposed monoanion (bdt(center dot-)) 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 (S-Fe = 0) and 2 has a medium-spin ferric ion (S-Fe = 1/2) and a low-spin ferrous center (S-Fe = 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.