Does a stabilising interaction favouring the Z,Z configuration of -S-N=S=N-S- systems exist?
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. The 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-Se-N=S=N-Se-Ph (2) in particular the isomeric equilibrium in solution found in the variable-temperature 77Se 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
Karla
K
Department of Chemistry, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk, Belgium.
Mandado
Marcos
M
Van Alsenoy
Christian
C
Bagryanskaya
Irina Yu
IY
Kovalev
Mikhail K
MK
Makarov
Alexander Yu
AY
Gatilov
Yuri V
YV
Shakirov
Makhmut M
MM
Zibarev
Andrey V
AV
Blockhuys
Frank
F