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Does a Stabilising Interaction Favouring the Z , Z Configuration of S‐NSN‐S Systems Exist?
Author(s) -
Tersago Karla,
Mandado Marcos,
Van Alsenoy Christian,
Bagryanskaya Irina Yu.,
Kovalev Mikhail K.,
Makarov Alexander Yu.,
Gatilov Yuri V.,
Shakirov Makhmut M.,
Zibarev Andrey V.,
Blockhuys Frank
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200500130
Subject(s) - gas phase , configuration interaction , chemistry , phase (matter) , crystallography , spectrum (functional analysis) , crystal structure , computational chemistry , stereochemistry , physics , quantum mechanics , molecule , organic chemistry
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‐NSN‐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‐NSN‐S‐ systems. For the analogous Ph‐Se‐NSN‐Se‐Ph ( 2 ) in particular the isomeric equilibrium in solution found in the variable‐temperature 77 Se 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.