The saga of rhodium(III) nitrate complexes and their speciation in solution: An integrated experimental and quantum chemical study Научная публикация
Журнал |
Polyhedron
ISSN: 1873-3719 , E-ISSN: 0277-5387 |
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Вых. Данные | Год: 2022, Том: 211, Страницы: 115564 Страниц : 11 DOI: 10.1016/j.poly.2021.115564 | ||
Ключевые слова | Rhodium X-ray diffraction NMR Speciation Kinetics Quantum chemical calculations | ||
Авторы |
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Организации |
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Реферат:
Rhodium(III) nitrate complexes trans-[(CH3)4N][Rh(H2O)2(NO3)4] (I), [(CH3)4N]Na2[Rh(H2O)6](NO3)6 (II),
[(C2H5)4N]2[Rh(H2O)(NO3)5] (III) and [(CH3)4N]2[Rh(H2O)(NO3)5] (IV) were synthesized by the reactions of a
“rhodium nitrate solution” with (CH3)4NNO3 and (C2H5)4NNO3. The complexes I, III and IV represent the first
examples of soluble rhodium(III) complexes having four and five coordinated nitrato ligands, while II is the first
example of a hexaaquarhodium(III) nitrate complex. Thermodynamic stability constants βi for the set of equilibria
[Rh(H2O)6]3+ + iNO3 = [Rh(H2O)(6-i)(NO3)i](3 i) + iH2O were estimated using rhodium(III) solutions
equilibrated for years. The constants decrease with the increase in the number of coordinated NO3 groups as
follows: β1 ≈ 100, β2cis ≈ 10 1, β2trans ≈ 10 1 – 10 2, β3mer ≈ 10 2, β3fac ≈ 10 2, β4cis ≈ 10 4, β4trans ≈ 10 4. The
kinetics and thermodynamics of NO3 ligands substitution with H2O molecules have been thoroughly studied by
DFT calculations for a series of [Rh(NO3)x(H2O)6–x](3 x) complexes (x = 0–6). The high solubility of the synthesized
complexes increases their synthetic significance and opens up new horizons in various practical applications
such as homogeneous catalysis, photo- and electrochemistry, drug discovery and bioinorganic
chemistry.
Библиографическая ссылка:
Vorobyeva S.N.
, Shekhovtsov N.A.
, Baidina I.A.
, Sukhikh T.S.
, Tkachev S.V.
, Bushuev M.B.
, Belyaev A.V.
The saga of rhodium(III) nitrate complexes and their speciation in solution: An integrated experimental and quantum chemical study
Polyhedron. 2022. V.211. P.115564. DOI: 10.1016/j.poly.2021.115564 WOS Scopus РИНЦ OpenAlex
The saga of rhodium(III) nitrate complexes and their speciation in solution: An integrated experimental and quantum chemical study
Polyhedron. 2022. V.211. P.115564. DOI: 10.1016/j.poly.2021.115564 WOS Scopus РИНЦ OpenAlex
Идентификаторы БД:
Web of science: | WOS:000719336700008 |
Scopus: | 2-s2.0-85118892617 |
РИНЦ: | 47523562 |
OpenAlex: | W3214341829 |