Intramolecular hydrogen-bonding in a cobalt aqua complex and electrochemical water oxidation activity† †Electronic supplementary information (ESI) available: General experimental details, synthetic methods, characterization, electrochemical data, gas chromatography, cif files. CCDC 1586338–1586341. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04960a
Water oxidation is catalysed in Nature by a redox cofactor embedded in a hydrogen-bonded network designed to orchestrate proton transfer throughout the challenging 4 electron reaction. Water oxidation is catalysed in Nature by a redox cofactor embedded in a hydrogen-bonded network designed to orches...
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Published in | Chemical science (Cambridge) Vol. 9; no. 10; pp. 2750 - 2755 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
Royal Society of Chemistry
06.02.2018
|
Subjects | |
Online Access | Get full text |
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Summary: | Water oxidation is catalysed in Nature by a redox cofactor embedded in a hydrogen-bonded network designed to orchestrate proton transfer throughout the challenging 4 electron reaction.
Water oxidation is catalysed in Nature by a redox cofactor embedded in a hydrogen-bonded network designed to orchestrate proton transfer throughout the challenging 4 electron reaction. In order to mimic aspects of this microenvironment, [CoL
DMA
(CH
3
CN)
2
][BF
4
]
2
(
2
) was synthesized, where L
DMA
is a dipyridyldiamine ligand with two dimethylamine bases in the secondary coordination sphere. Structural characterization of the corresponding aqua complexes establish hydrogen bonding between the bound water and pendant base(s). Cyclic voltammetry of [CoL
DMA
(CH
3
CN)
2
][BF
4
]
2
(
2
) reveals enhanced oxidative current upon titration with water and controlled potential electrolysis confirms evolution of O
2
. The related complex [CoL
H
(CH
3
CN)
2
][BF
4
]
2
(
1
), which has the same primary coordination environment as
2
but lacks pendant bases, is inactive. The structural and electrochemical studies illustrate the role positioned proton relays can play in promoting redox reactivity. |
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ISSN: | 2041-6520 2041-6539 |
DOI: | 10.1039/c7sc04960a |