Abstract
The present work uncovers the oxidative transformations of a recently reported polypyridyl phosphonate-phenoxo Ru-based water oxidation catalyst [RuIII(tPaO-κ-N2OPOC)(py)2]2-, 22- {tPaO5- is the 3-(hydroxo-[2,2′:6′,2″-terpyridine]-6,6″-diyl)bis(phosphonate)}, under turnover conditions. We show how the catalyst 22- suffers from oxidative degradation during water oxidation catalysis and generates the phosphonate-carboxylate Ru complex [RuII(Hbpc)(py)2], 3H, where bpc3- is 6′-phosphonato-[2,2′-bipyridine]-6-carboxylate. Complex 3H has been prepared by three different methods, and its oxidative transformations were also studied in detail. Under turnover conditions, complex 3H undergoes a series of transformations that can be monitored by electrochemical techniques including the generation of catalytically active molecular water oxidation catalyst intermediates and RuO2. In addition, catalytically inactive species such as [RuII(bpc-κ-N2OP)2] have also been detected.
Original language | English |
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Pages (from-to) | 5240-5247 |
Number of pages | 8 |
Journal | ACS catalysis |
Volume | 11 |
Issue number | 9 |
DOIs | |
Publication status | Published - 7 May 2021 |
Keywords
- electrocatalysis
- molecular catalyst
- oxidative decomposition
- redox catalysis
- Ru complexes
- water oxidation
- water splitting
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CCDC 2045432: Experimental Crystal Structure Determination
Vereshchuk, N. (Creator), Holub, J. (Contributor), Gil-Sepulcre, M. (Contributor), Benet-Buchholz, J. (Contributor) & Llobet, A. (Contributor), Cambridge Crystallographic Data Centre, 19 Nov 2020
DOI: 10.5517/ccdc.csd.cc26nfp0, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc26nfp0&sid=DataCite
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CCDC 2044298: Experimental Crystal Structure Determination
Vereshchuk, N. (Creator), Holub, J. (Contributor), Gil-Sepulcre, M. (Contributor), Benet-Buchholz, J. (Contributor) & Llobet, A. (Contributor), Cambridge Crystallographic Data Centre, 13 Nov 2020
DOI: 10.5517/ccdc.csd.cc26m837, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc26m837&sid=DataCite
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