DFT study and dynamic NMR evidence for cis-trans conformational isomerism in square planar Ni(II) thioselenophosphinate, Ni(SeSPPh2)(2) Научная публикация
Журнал |
Journal of Organometallic Chemistry
ISSN: 0022-328X |
||||||||
---|---|---|---|---|---|---|---|---|---|
Вых. Данные | Год: 2014, Том: 768, Страницы: 151-156 Страниц : DOI: 10.1016/j.jorganchem.2014.06.013 | ||||||||
Ключевые слова | Nickel; DFT calculations; VT P-31 NMR; Spin-crossover; Thioselenophosphinate | ||||||||
Авторы |
|
||||||||
Организации |
|
Реферат:
Theoretical (DFT) and experimental (dynamic NMR) study of cis-trans conformational isomerism in Ni(II) square planar thioselenophosphinate, Ni(SeSPPh2)(2), have been carried out. The OFT investigation [B3LYP/6-311++G(d,p), gas] of this complex reveals that its cis-to-trans isomerization occurs through two minimal energy crossing points (MECPs) located at the intersection of the lowest singlet and triplet PESs (potential energy surfaces). The calculated relative energies of the MECPs, 5.6 and 3.6 kcal/mol, correspond to low-energy barriers of "cis-Ni(SeSPPh2)(2) [S] (sic) pseudoterahedral-Ni(SeSPPM2)(2) [T]" and "trans-Ni(SeSPPh2)(2) [S] (sic) pseudoterahedral-Ni(SeSPPM2)(2) [T]" spin crossover rearrangements. The dynamic P-31 NMR study of Ni(SeSPPh2)(2) is fully confirms these computations: below 208 K, the cis- and trans-isomers are in a dynamic equilibrium. The free energy of activation for this fluxional process calculated from the coalescence temperature is Delta G(not equal) = 11.5 kcal/mol. (C) 2014 Elsevier B.V. All rights reserved.
Библиографическая ссылка:
Artem'ev A.V.
, Shagun V.A.
, Gusarova N.K.
, Liu C.W.
, Liao J-H.
, Gatilov Y.V.
, Trofimov B.A.
DFT study and dynamic NMR evidence for cis-trans conformational isomerism in square planar Ni(II) thioselenophosphinate, Ni(SeSPPh2)(2)
Journal of Organometallic Chemistry. 2014. V.768. P.151-156. DOI: 10.1016/j.jorganchem.2014.06.013 WOS Scopus РИНЦ OpenAlex
DFT study and dynamic NMR evidence for cis-trans conformational isomerism in square planar Ni(II) thioselenophosphinate, Ni(SeSPPh2)(2)
Journal of Organometallic Chemistry. 2014. V.768. P.151-156. DOI: 10.1016/j.jorganchem.2014.06.013 WOS Scopus РИНЦ OpenAlex
Даты:
Опубликована в печати: | 1 окт. 2014 г. |
Идентификаторы БД:
Web of science: | WOS:000340853500019 |
Scopus: | 2-s2.0-84904873250 |
РИНЦ: | 23969886 |
OpenAlex: | W2005342863 |