title: Two-electron reduction of a Rh-Mo-Rh dithiolato complex to form a triplet ground state associated with a change in CO coordination mode.
abstract: We synthesized a dithiolato-bridged heterometal trinuclear complex [{(eta(5)-C(5)Me(5))Rh(S(2)C(6)H(4))}(2)Mo(CO)(2)] (1) in which two rhodadithiolene complex units are bridged by a Mo(CO)(2) moiety. Complex 1 with a Rh(III)-Mo(0)-Rh(III) bond exhibits reversible one-step two-electron reduction with potential inversion. This redox process between 1 and 1(2-) accompanies a reversible structural change, which is an alternation in the CO coordination mode between semibridging and bridging. The ground state of dianion 1(2-) with a Rh(II)-Mo(0)-Rh(II) bond is assigned to spin triplet. These alternations of CO coordination mode and spin state are fully consistent with the density functional theory calculation results. This is the first example of multinuclear metalladithiolene complex which was successful in elucidating a reversible multielectron redox process associated with structural change and spin state change.
authors.affiliation: Department of Chemistry, School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-Ku, Tokyo, 113-0033, Japan.
authors.forename: Satoshi
authors.initials: S
authors.lastname: Muratsugu
authors.forename: Keitaro
authors.initials: K
authors.lastname: Sodeyama
authors.forename: Fusao
authors.initials: F
authors.lastname: Kitamura
authors.forename: Manabu
authors.initials: M
authors.lastname: Sugimoto
authors.forename: Shinji
authors.initials: S
authors.lastname: Tsuneyuki
authors.forename: Seiji
authors.initials: S
authors.lastname: Miyashita
authors.forename: Tatsuhisa
authors.initials: T
authors.lastname: Kato
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Nishihara
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry*; D004583:Electrons; D008958:Models, Molecular; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D010084:Oxidation-Reduction; D012238:Rhodium / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D013438:Sulfhydryl Compounds; D002248:Carbon Monoxide; D008982:Molybdenum; D012238:Rhodium