Conformational isomerism of the seven-membered heterocycle in a single crystal of [η2-Ph2P(O)(CH2)2C(O)NМе2]TiF4 adduct
- Authors: Il’in E.G.1, Parshakov A.S.1, Aleksandrov G.G.1, Yarzhemskii V.G.1, Danilov V.V.1, Bodrin G.V.2, Goryunov E.I.2, Nifantev E.E.2
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Affiliations:
- Kurnakov Institute of General and Inorganic Chemistry
- Nesmeyanov Institute of Organoelement Compounds
- Issue: Vol 470, No 1 (2016)
- Pages: 255-259
- Section: Chemistry
- URL: https://journals.rcsi.science/0012-5008/article/view/153757
- DOI: https://doi.org/10.1134/S0012500816090068
- ID: 153757
Cite item
Abstract
The crystal structure of TiF4[(Ph2P(O)CH2CH2C(O)NMe2)] chelate (I) was studied by X-ray crystallography, which revealed four crystallographically independent complex molecules of similar structure (1–4). It was found that the molecules are only slightly different in the bond lengths between the coordinated atoms and the central titanium ion and considerably different in the geometry of the seven-membered TiOPCCCO chelate ring. The geometry of the chelate rings was found to be almost identical in each pair of complexes 1, 2 (A) and 3, 4 (B), and a conclusion was drawn on the presence of two conformational isomers (A and B) of the chelate complex. Quantum chemical calculations of the relative thermodynamic stability of molecules 1–4 were performed, and their geometry optimization led to one theoretical structure. The comparison of the chelate ring geometry in the theoretical structure and in conformers A and B revealed that the conformation of the theoretical chelate ring coincides with that of conformer A.
About the authors
E. G. Il’in
Kurnakov Institute of General and Inorganic Chemistry
Author for correspondence.
Email: eg_ilin@mail.ru
Russian Federation, Leninskii pr. 31, Moscow, 119991
A. S. Parshakov
Kurnakov Institute of General and Inorganic Chemistry
Email: eg_ilin@mail.ru
Russian Federation, Leninskii pr. 31, Moscow, 119991
G. G. Aleksandrov
Kurnakov Institute of General and Inorganic Chemistry
Email: eg_ilin@mail.ru
Russian Federation, Leninskii pr. 31, Moscow, 119991
V. G. Yarzhemskii
Kurnakov Institute of General and Inorganic Chemistry
Email: eg_ilin@mail.ru
Russian Federation, Leninskii pr. 31, Moscow, 119991
V. V. Danilov
Kurnakov Institute of General and Inorganic Chemistry
Email: eg_ilin@mail.ru
Russian Federation, Leninskii pr. 31, Moscow, 119991
G. V. Bodrin
Nesmeyanov Institute of Organoelement Compounds
Email: eg_ilin@mail.ru
Russian Federation, ul. Vavilova 28, Moscow, 119991
E. I. Goryunov
Nesmeyanov Institute of Organoelement Compounds
Email: eg_ilin@mail.ru
Russian Federation, ul. Vavilova 28, Moscow, 119991
E. E. Nifantev
Nesmeyanov Institute of Organoelement Compounds
Email: eg_ilin@mail.ru
Russian Federation, ul. Vavilova 28, Moscow, 119991