Release Time:2019-03-13  Hits:

Indexed by: Journal Article

Date of Publication: 2016-09-01

Journal: CHINESE JOURNAL OF CHEMISTRY

Included Journals: Scopus、SCIE

Volume: 34

Issue: 9

Page Number: 919-924

ISSN: 1001-604X

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

Abstract: 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.