Influence of the polarization effect on the donor properties of 1-phenylsilatrane
- Authors: Tandura S.N.1, Belyaeva V.V.2, Gostevskii B.A.2, Albanov A.I.2
-
Affiliations:
- N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
- A. E. Favorsky Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences
- Issue: Vol 66, No 12 (2017)
- Pages: 2269-2275
- Section: Full Article
- URL: https://journals.rcsi.science/1066-5285/article/view/241768
- DOI: https://doi.org/10.1007/s11172-017-2013-3
- ID: 241768
Cite item
Abstract
A new mechanism of the dipole—induced dipole polarization interaction was considered to explain an anomalous increase in the +I effect in a 1-phenylsilatrane molecule with the pentacoordinated Si atom. The interaction through the space between the silatrane cage having a high dipole moment and easily polarizable aromatic phenyl substituent induces dipole that adds the influence of the inductive effect along the bonds, which is characteristic of usual silatranes. The high inductive constant σI calculated for 1-phenylsilatrane on the basis of chemical shifts δC of aromatic carbon atoms was interpreted as a superelectronodonor effect in silatranes. However, the polarization effect through the space leads to a substantial change in the chemical shifts δC for the phenyl group in the direction that formally corresponds to the enhancement of the +I effect transmitted via the bonds. It is shown for the first time that the inductive effect in silatranes is not constant and varies according to the polarizability of the substituent at the Si atom.
About the authors
S. N. Tandura
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
Email: belyaevav@irioch.irk.ru
Russian Federation, 47 Leninsky prosp., Moscow, 119991
V. V. Belyaeva
A. E. Favorsky Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences
Author for correspondence.
Email: belyaevav@irioch.irk.ru
Russian Federation, 1 ul. Favorskogo, Irkutsk, 664033
B. A. Gostevskii
A. E. Favorsky Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences
Email: belyaevav@irioch.irk.ru
Russian Federation, 1 ul. Favorskogo, Irkutsk, 664033
A. I. Albanov
A. E. Favorsky Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences
Email: belyaevav@irioch.irk.ru
Russian Federation, 1 ul. Favorskogo, Irkutsk, 664033