Preparation of Rhodium(III) cis-Diaquacomplex by a Protic Acid Induced Oxalate-Releasing from mer-[Rh(C2O4)Cl(py)3]
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
New Journal of Chemistry
ISSN: 1144-0546
, E-ISSN: 1369-9261
|
| Вых. Данные |
Год: 2018,
Том: 42,
Номер: 24,
Страницы: 19637-19643
Страниц
: 7
DOI:
10.1039/C8NJ04264K
|
| Ключевые слова |
PRODUCTION UTILIZING IRIDIUM; WATER REDUCTION; OXYGEN-EXCHANGE; COMPLEXES; CATALYSTS; COORDINATION; SYSTEM |
| Авторы |
Vasilchenko Danila
1,2
,
Tkachev Sergey
1
,
Baidina Iraida
1
,
Korolkov Ilya V.
1
,
Berdyugin Semen
1
,
Kozlova Ekaterina
2,3
,
Kozlov D
2,3
|
| Организации |
| 1 |
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Science, 630090 Novosibirsk, Russian Federation
|
| 2 |
Novosibirsk State University, 630090 Novosibirsk, Russian Federation
|
| 3 |
Boreskov Institute of Catalysis, 630090 Novosibirsk, Russia
|
|
Информация о финансировании (2)
|
1
|
Министерство науки и высшего образования Российской Федерации
|
ГЗ-2017-2020
|
|
2
|
Совет по грантам Президента Российской Федерации
|
|
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).