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Evidence of proton-coupled mixed-valency by electrochemical behavior on transition metal complex dimers bridged by two Ag+ ions

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Abstract

H-Bonded metal complex dimers with reversible redox behaviour, which are connected by a low-barrier hydrogen bond (LBHB) with a very low energy barrier for proton transfer, can provide a unique mixed-valency state stabilized by the proton-coupled electron transfer (PCET) phenomenon. Using cyclic voltammetry measurements, newly prepared [ReIIICl2(PnPr3)2(Hbim)]2 (2) and [OsIIICl2(PnPr3)2(Hbim)]2 (3) existing as H-bonded dimers in a CH2Cl2 solution showed a four-step and four-electron transfer containing two mixed-valency states of ReIIReIII and ReIIIReIV, and OsIIOsIII and OsIIIOsVI, respectively. Furthermore, [ReIIICl2(PnPr3)2(Agbim)]2 (4) and [OsIIICl2(PnPr3)2(Agbim)]2 (5), bridged by two Ag+ ions instead of two H-bonding protons, were prepared, and their electrochemical behaviours changed to a two-step and four-electron transfer. It is clear that the H-bonded complex dimers 2 and 3, connected by an LBHB, can be electrochemically stabilized into unique pairs of mixed-valency states by PCET, and the H-bonding proton transfer also controls the electrochemical redox behaviour.

Graphical abstract: Evidence of proton-coupled mixed-valency by electrochemical behavior on transition metal complex dimers bridged by two Ag+ ions

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Publication details

The article was received on 02 Oct 2018, accepted on 15 Nov 2018 and first published on 07 Dec 2018


Article type: Paper
DOI: 10.1039/C8DT03962C
Citation: Dalton Trans., 2019, Advance Article
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    Evidence of proton-coupled mixed-valency by electrochemical behavior on transition metal complex dimers bridged by two Ag+ ions

    M. Tadokoro, K. Isogai, S. Harada, T. Kouchi, T. Yamane, T. Sugaya and H. Kamebuchi, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C8DT03962C

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