Correlation among the Gas-Phase, Solution, and Solid-Phase Geometrical and NMR Parameters of Dative Bonds in the Pentacoordinate Silicon Compounds. 1‑Substituted Silatranes

Silatranes XSi(OCH2CH2)3N exhibit a good linear relationship between their experimental and calculated (IGLO and GIAO) values of the NMR chemical shifts of 15N, δN, and the lengths of dative bonds Si←N, d SiN, determined in the gas phase (ED, CCSD), solutions (COSMO PBE0, B3PW91), and crystals (X-ra...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2013-06, Vol.117 (25), p.5365-5376
Main Authors: Belogolova, Elena F, Sidorkin, Valery F
Format: Article
Language:English
Subjects:
Aggregates
Chemical bonds
Contact
Crystals
Mathematical analysis
Nuclear magnetic resonance
Silicon compounds
X-rays
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Summary:Silatranes XSi(OCH2CH2)3N exhibit a good linear relationship between their experimental and calculated (IGLO and GIAO) values of the NMR chemical shifts of 15N, δN, and the lengths of dative bonds Si←N, d SiN, determined in the gas phase (ED, CCSD), solutions (COSMO PBE0, B3PW91), and crystals (X-ray). An aggregate of the obtained data provides strong evidence that the gas-phase value of d SiN in MeSi(OCH2CH2)3N should be greater by ∼0.05 Å than that determined in the electron diffraction (ED) experiment (2.45 Å). Given this condition, a long-standing contradiction between the data of the structural (X-ray, ED) and NMR 15N experiments for the molecules of 1-methyl- and 1-fluorosilatrane regarding the sensitivity of their coordination contact Si←N to the medium effect is resolved.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp4035216