Structural Manifestations of the Polarizability Effect in 1-Halogensilatranes According to the Dipole-Induced Dipole Mechanism
| Autor: | S. N. Tandura, V. V. Belyaeva, V. P. Baryshok, Vladimir I. Smirnov, B. A. Gostevsky |
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| Rok vydání: | 2019 |
| Předmět: |
Physics
Solid-state physics Chemical shift 010402 general chemistry 010403 inorganic & nuclear chemistry 01 natural sciences Molecular physics 0104 chemical sciences Inorganic Chemistry Bond length Dipole Polarizability Moment (physics) Atom Materials Chemistry Physics::Atomic Physics Physical and Theoretical Chemistry Inductive effect |
| Zdroj: | Journal of Structural Chemistry. 60:932-941 |
| ISSN: | 1573-8779 0022-4766 |
| DOI: | 10.1134/s0022476619060076 |
| Popis: | A new mechanism of the dipole-induced dipole polarizability effect by the example of 1-halogensilatranes is proposed. The mechanism involves a through-space interaction between the dipole moment μ of the core and the dipole Δμ which is induced on the halogen and, in turn, induces an extra dipole ΔΔμ on the transannular bond Si ← N to make it stronger. This effect explains for the first time the previously discovered contradiction for 1-halogensilatranes where an inverse dependence in the linear correlations between the Si ← N bond length, δ15N, δ1H(CH2N) chemical shifts, and the inductive constant σ are observed. For example, the length of the Si ← N coordination bond is shorter in 1-chlorosilatranе than in 1-fluorosilatrane due to the fact that the polarizability effect is stronger than the inductive effect in the case of the Cl atom. |
| Databáze: | OpenAIRE |
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