The nature of the intramolecular transannular Si···N interaction in crystalline 1-methylsilatrane, as found from X-ray diffraction data

Silatranes XSi(OCH2CH2)3N exhibit a good linear relationship between their experimental and calculated (IGLO and GIAO) values of the NMR chemical shifts of (15)N, δN, and the lengths of dative bonds Si←N, dSiN, 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 dSiN 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 (15)N 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.

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“… a All calculations were performed with the 6-311G(d,p) basis set. b Reference . c Reference d Reference . …”

Section: Resultsmentioning

confidence: 99%

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

Belogolova

Sidorkin

2013

J. Phys. Chem. A

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“…Nevertheless, it is worthy to note that the electron density at the BCP between Si and N is similar to that for Si-Cl. A very recent determination of the deformation 36 electron density in crystalline methylsilatrane makes a comparison of these results with experiment possible. Lyssenko et al confirm the existence of a BCP between Si and N and determine the electron density at this point to be 0.42 e Å -3 , in excellent agreement with the value for the chloro compound calculated with cluster 3.…”

Section: Resultsmentioning

confidence: 99%

A Quantum Mechanical Investigation of the Nature of the Dative Bond in Crystalline 1-Chlorosilatrane

Dillen¹

2004

J. Phys. Chem. A

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The molecular geometry of crystalline 1-chlorosilatrane is computed at the self-consistent field (SCF) and density functional theory (DFT) levels of theory with the 6-31G* basis set and compared with experiment. The calculations reproduce the shortening of the Si-N distance in the crystal relative to the gas phase, in agreement with existing experimental data for methyl-and fluorosilatrane. The bond shortening is shown to be the result of a combination of a conformational change in the molecule and dipole-dipole interactions with the surrounding molecules in the crystal. The importance of the need to include long-range interactions in the calculation is demonstrated. The calculated electron density of chlorosilatrane is analyzed in terms of the natural bond orbital formalism (NBO), natural resonance theory (NRT), and the theory of atoms in molecules (AIM).

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“…Therefore, according to mentioned classification of atomic interactions, this bond was considered as an interaction of intermediate type. Positive value of ∇ 2 ρ( r ) was found also in the CP(3,−1) for the Si···N interaction in 1-methylsilatrane (data were obtained with MP2/6-31G(d) calculations and from an experimental EDD study , ). Despite that evaluation of E ( r ) was not carried out, − the absolute values of ρ( r ) and ∇ 2 ρ( r ) in the CP's(3,−1) for both B−N and Si−N bonds allowed one to make a preliminary conclusion that both these bonds correspond to the intermediate type of interatomic interaction.…”

Section: Introductionmentioning

confidence: 91%

Experimental and Theoretical Study of the Transannular Intramolecular Interaction and Cage Effect in the Atrane Framework of Boratrane and 1-Methylsilatrane

et al. 2002

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On the basis of the high-resolution single-crystal X-ray diffraction data and theoretical B3LYP/6-311+G(d) and B3LYP/cc-pVDZ calculations, the electron density distribution in boratrane and 1-methylsilatrane has been investigated. The B-N bond in the boratrane molecule was found to correspond to the "shared" (covalent) interatomic interaction in terms of Bader's "atoms in molecules" (AIM) theory. On the contrary, the Si...N bond in 1-methylsilatrane and B-N bond in a series of some acyclic donor-acceptor boron complexes and other boratrane derivatives correspond to interaction of an "intermediate" type. Such character of the B-N bond is caused by an influence of the atrane "cage effect". The influence of this effect results in deformation of the boron atom and displacement of the bond critical point (3,-1) to the region of the electron lone pair of the nitrogen atom. This changes the type of the interatomic interaction in comparison to other compounds investigated and explains high hydrolytic stability of boratrane as well as silatranes and germatranes.

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The nature of the intramolecular transannular Si···N interaction in crystalline 1-methylsilatrane, as found from X-ray diffraction data

Cited by 28 publications

References 16 publications

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

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

A Quantum Mechanical Investigation of the Nature of the Dative Bond in Crystalline 1-Chlorosilatrane

Experimental and Theoretical Study of the Transannular Intramolecular Interaction and Cage Effect in the Atrane Framework of Boratrane and 1-Methylsilatrane

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