Influence of the polarization effect on the donor properties of 1-phenylsilatrane
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 easil...
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Veröffentlicht in: | Russian chemical bulletin 2017-12, Vol.66 (12), p.2269-2275 |
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Hauptverfasser: | , , , |
Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | 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 σ
I
calculated for 1-phenylsilatrane on the basis of chemical shifts δ
C
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 δ
C
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. |
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ISSN: | 1066-5285 1573-9171 |
DOI: | 10.1007/s11172-017-2013-3 |