Preparation of Rhodium(III) cis-Diaquacomplex by a Protic Acid Induced Oxalate-Releasing from mer-[Rh(C2O4)Cl(py)3] Full article
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New Journal of Chemistry
ISSN: 1144-0546 , E-ISSN: 1369-9261 |
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| Output data | Year: 2018, Volume: 42, Number: 24, Pages: 19637-19643 Pages count : 7 DOI: 10.1039/C8NJ04264K | ||||||
| Tags | PRODUCTION UTILIZING IRIDIUM; WATER REDUCTION; OXYGEN-EXCHANGE; COMPLEXES; CATALYSTS; COORDINATION; SYSTEM | ||||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Ministry of Science and Higher Education of the Russian Federation | ГЗ-2017-2020 |
| 2 | Council for Grants of the President of the Russian Federation |
Abstract:
The neutral rhodium(III) mer-[Rh(C2O4)Cl(py)3] (1) complex was found to release oxalate in concentrated aqueous solutions of strong acids (HNO3, HClO4, CF3SO3H), generating the heteroleptic cis-diaquacomplex cis,mer-[RhCl(H2O)2(py)3]2+ (3). The process proceeded via formation of intermediate complex 2 ([Rh(HC2O4)Cl(H2O)(py)3]+) with the monodentately coordinated oxalato ligand. The structure of the intermediate complex 2 was probed using density functional theory (DFT) calculations. Experimental 13C nuclear magnetic resonance (NMR) data on the kinetics of oxalate releasing at 25°C were evaluated within a consecutive reaction model with two pseudo-first order stages. The logarithms of the rate constants linearly depended on the Hammett acidity function of the medium. Cationic cis-diaquacomplex 3 was found to act as an active water reduction catalyst (WRC) under visible light irradiation when paired with the [Ir(ppy)2bpy]+ photosensitizer (PS).
Cite:
Vasilchenko D.
, Tkachev S.
, Baidina I.
, Korolkov I.V.
, Berdyugin S.
, Kozlova E.
, Kozlov D.
Preparation of Rhodium(III) cis-Diaquacomplex by a Protic Acid Induced Oxalate-Releasing from mer-[Rh(C2O4)Cl(py)3]
New Journal of Chemistry. 2018. V.42. N24. P.19637-19643. DOI: 10.1039/C8NJ04264K WOS Scopus РИНЦ AN OpenAlex
Preparation of Rhodium(III) cis-Diaquacomplex by a Protic Acid Induced Oxalate-Releasing from mer-[Rh(C2O4)Cl(py)3]
New Journal of Chemistry. 2018. V.42. N24. P.19637-19643. DOI: 10.1039/C8NJ04264K WOS Scopus РИНЦ AN OpenAlex
Dates:
| Submitted: | Aug 21, 2018 |
| Accepted: | Nov 6, 2018 |
| Published online: | Nov 7, 2018 |
| Published print: | Dec 21, 2018 |
Identifiers:
| Web of science: | WOS:000456501100036 |
| Scopus: | 2-s2.0-85057720059 |
| Elibrary: | 38627006 |
| Chemical Abstracts: | 2018:2110403 |
| OpenAlex: | W2900401080 |