Does a stabilising interaction favouring the Z,Z configuration of -S-N=S=N-S-systems exist?

Does a stabilising interaction favouring the Z,Z configuration of -S-N=S=N-S-systems exist? Full article

Journal

Chemistry - A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765

Output data

Year: 2005, Volume: 11, Number: 15, Pages: 4544-4551 Pages count : 8 DOI: 10.1002/chem.200500130

Tags

chalcogen-nitrogen chains; density functional calculations; intramolecular interactions; X-ray diffraction

Authors

Tersago K ¹ , Mandado M ¹ , Van Alsenoy C ¹ , Bagryanskaya IY ² , Kovalev MK ⁴ , Makarov AY ² , Gatilov YV ² , Shakirov MM ² , Zibarev AV ^2,3 , Blockhuys F ¹

Affiliations

1	(Данные Web of science) Univ Antwerp, Dept Chem, B-2610 Antwerp, Belgium
2	(Данные Web of science) Russian Acad Sci, Inst Organ Chem, Novosibirsk 630090, Russia
3	(Данные Web of science) Novosibirsk State Univ, Dept Nat Sci, Novosibirsk 630090, Russia
4	(Данные Web of science) Novosibirsk State Univ, Dept Phys, Novosibirsk 630090, Russia

The existence of the orbital interaction presented in the literature as being the cause for the stabilisation of the Z,Z configuration of Ph-S-N=S-N-S-Ph (1) and its derivatives in the crystal phase, has been investigated. ne results of theoretical calculations at the DFT/B3LYP/6-311+G* level of theory suggest that such a stabilising interaction might not exist or be extremely weak and that packing forces must be the main cause of the observed Z,Z configuration in the solid. To reach this conclusion structural and energetic parameters were combined to study the bonding in these -S-N=S=N-S- systems. For the analogous Ph-SeN=S=N-Se-Ph (2) in particular the isomeric equilibrium in solution found in the variable-temperature Se-77 NMR spectrum indicates that, in the gas phase or in solution, the observed Z,Z configuration is not stabilised to a greater extent than the Z,E configuration.

Tersago K. , Mandado M. , Van Alsenoy C. , Bagryanskaya I. , Kovalev M. , Makarov A. , Gatilov Y. , Shakirov M. , Zibarev A. , Blockhuys F.
Does a stabilising interaction favouring the Z,Z configuration of -S-N=S=N-S-systems exist?
Chemistry - A European Journal. 2005. V.11. N15. P.4544-4551. DOI: 10.1002/chem.200500130 WOS Scopus РИНЦ

Published online:	May 18, 2005
Published print:	Jul 18, 2005

Web of science	WOS:000230761400024
Scopus	2-s2.0-22944432542
Elibrary	13476707
OpenAlex	W2142513074