DFT study and dynamic NMR evidence for cis-trans conformational isomerism in square planar Ni(II) thioselenophosphinate, Ni(SeSPPh2)(2)

DFT study and dynamic NMR evidence for cis-trans conformational isomerism in square planar Ni(II) thioselenophosphinate, Ni(SeSPPh2)(2) Full article

Journal

Journal of Organometallic Chemistry
ISSN: 0022-328X

Output data

Year: 2014, Volume: 768, Pages: 151-156 Pages count : DOI: 10.1016/j.jorganchem.2014.06.013

Tags

Nickel; DFT calculations; VT P-31 NMR; Spin-crossover; Thioselenophosphinate

Authors

Artem'ev Alexander V. ¹ , Shagun Vladimir A. ¹ , Gusarova Nina K. ¹ , Liu C. W. ² , Liao Jian-Hong ² , Gatilov Yurii V. ^3,4 , Trofimov Boris A. ¹

Affiliations

1	(Данные Web of science) Russian Acad Sci, Siberian Branch, AE Favorsky Irkutsk Inst Chem, Irkutsk 664033, Russia
2	(Данные Web of science) Natl Dong Hwa Univ, Dept Chem, Hualien 97401, Taiwan
3	(Данные Web of science) Russian Acad Sci, Siberian Branch, NN Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia
4	(Данные Web of science) Novosibirsk State Univ, Novosibirsk 630090, Russia

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.

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

Published print:

Oct 1, 2014

Web of science:	WOS:000340853500019
Scopus:	2-s2.0-84904873250
Elibrary:	23969886
OpenAlex:	W2005342863

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Scopus	10
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