Two-Electron Reduction of a Rh−Mo−Rh Dithiolato Complex To Form a Triplet Ground State Associated with a Change in CO Coordination Mode

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• 作者：Satoshi Muratsugu ; Keitaro Sodeyama ; Fusao Kitamura ; Manabu Sugimoto ; Shinji Tsuneyuki ; Seiji Miyashita ; Tatsuhisa Kato ; Hiroshi Nishihara
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：February 4, 2009
• 年：2009
• 卷：131
• 期：4
• 页码：1388-1389
• 全文大小：143K
• 年卷期：v.131,no.4(February 4, 2009)
• ISSN：1520-5126

文摘

We synthesized a dithiolato-bridged heterometal trinuclear complex [{(η⁵-C₅Me₅)Rh(S₂C₆H₄)}₂Mo(CO)₂] (1) in which two rhodadithiolene complex units are bridged by a Mo(CO)₂ moiety. Complex 1 with a Rh^III−Mo⁰−Rh^III bond exhibits reversible one-step two-electron reduction with potential inversion. This redox process between 1 and 1²⁻ accompanies a reversible structural change, which is an alternation in the CO coordination mode between semibridging and bridging. The ground state of dianion 1²⁻ with a Rh^II−Mo⁰−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.