Two-electron reduction of a Rh-Mo-Rh dithiolato complex to form a triplet ground state associated with a change in CO coordination mode.
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.
Muratsugu
Satoshi
S
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-Ku, Tokyo, 113-0033, Japan.
Sodeyama
Keitaro
K
Kitamura
Fusao
F
Sugimoto
Manabu
M
Tsuneyuki
Shinji
S
Miyashita
Seiji
S
Kato
Tatsuhisa
T
Nishihara
Hiroshi
H
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*
D013438:Sulfhydryl Compounds; D002248:Carbon Monoxide; D008982:Molybdenum; D012238:Rhodium