title: Development of a versatile synthesis method for trinuclear Co(iii), Rh(iii), and Ir(iii) dithiolene complexes, and their crystal structures and multi-step redox properties.
abstract: Triangular trinuclear Co(iii), Rh(iii), and Ir(iii) dithiolene complexes, [[M(3)(eta(5)-C(5)Me(5))(3)(S(6)C(6))] (M = Co, Rh, Ir), which have not been obtained by the trimerization of mononuclear complexes, were synthesized via a new synthetic route, that is, the reaction of benzenehexathiol and [(eta(5)-C(5)Me(5))Co(CO)I(2)], [Rh(eta(5)-C(5)Me(5))Cl(2)](2) and [Ir(eta(5)-C(5)Me(5))Cl(2)](2), respectively, under basic conditions. Single crystal X-ray diffraction measurements were carried out and their crystal structures were determined. Electrochemical measurements revealed that the trinuclear complexes exhibit three-step one-electron redox reactions and form mixed valence complexes. Studies on the stabilities of their mixed valence states and the X-ray crystal structure analyses revealed that the through-bond internuclear electronic interaction and the aromaticity of central benzene ring decrease in the order of Co > Rh > Ir.
authors.affiliation: Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Shibata
authors.forename: Baohua
authors.initials: B
authors.lastname: Zhu
authors.forename: Shoko
authors.initials: S
authors.lastname: Kume
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Nishihara