Structure and Conformational Analysis of 5,5-Bis(bromomethyl)-2,2-diphenyl-1,3-dioxane

Khazhiev, Sh. Yu.; Khusainov, M. A.; Khalikov, R. A.; Катаев, В. А.; Tyumkina, T. V.; Mescheryakova, Ekaterina S.; Халилов, Л. М.; Кузнецов, В. В.

doi:10.1134/s1070428020010017

Cited by 11 publications

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“…In all cases, the guest molecule has a negative electric charge. It should be stressed that the conformational behavior of substituted 1,3-dioxanes in usual solvents is not accompanied by the inversion of stability between the chair and any other form; in all cases, C-conformer remains the main minimum, and the role of the medium is relegated only to the It should be stressed that the conformational behavior of substituted 1,3-dioxanes in usual solvents is not accompanied by the inversion of stability between the chair and any other form; in all cases, C-conformer remains the main minimum, and the role of the medium is relegated only to the shift of the conformational equilibrium towards the chair-form with more or less polarity, due to the axial or equatorial orientation of polar substituents or with lower steric restriction [214,215]. In sharp contrast, the conformational properties of unsubstituted 1,3-dioxane in the SWCNT cavity are caused by the action of a new driving force, which can dramatically alter conformational properties of the guest cyclic molecules in comparison with those in the gas phase or in the usual solvents.…”

Section: 3-dioxane In Nanotubesmentioning

confidence: 99%

“…In the case of free 1,3-dioxa-2-silacyclohexane, C 3 H 8 SiO 2 (R=H), the corresponding ∆G 298 is 4.1 kcal/mol (PBE/3ζ) [220]. shift of the conformational equilibrium towards the chair-form with more or less polarity, due to the axial or equatorial orientation of polar substituents or with lower steric restriction [214,215]. In sharp contrast, the conformational properties of unsubstituted 1,3-dioxane in the SWCNT cavity are caused by the action of a new driving force, which can dramatically alter conformational properties of the guest cyclic molecules in comparison with those in the gas phase or in the usual solvents.…”

Section: 3-dioxa-2-silacyclohexane In Nanotubesmentioning

confidence: 99%

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Stereochemistry of Simple Molecules inside Nanotubes and Fullerenes: Unusual Behavior of Usual Systems

Кузнецов

2020

Molecules

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Over the past three decades, carbon nanotubes and fullerenes have become remarkable objects for starting the implementation of new models and technologies in different branches of science. To a great extent, this is defined by the unique electronic and spatial properties of nanocavities due to the ramified π-electron systems. This provides an opportunity for the formation of endohedral complexes containing non-covalently bonded atoms or molecules inside fullerenes and nanotubes. The guest species are exposed to the force field of the nanocavity, which can be described as a combination of electronic and steric requirements. Its action significantly changes conformational properties of even relatively simple molecules, including ethane and its analogs, as well as compounds with C−O, C−S, B−B, B−O, B−N, N−N, Al−Al, Si−Si and Ge−Ge bonds. Besides that, the cavity of the host molecule dramatically alters the stereochemical characteristics of cyclic and heterocyclic systems, affects the energy of pyramidal nitrogen inversion in amines, changes the relative stability of cis and trans isomers and, in the case of chiral nanotubes, strongly influences the properties of R- and S-enantiomers. The present review aims at primary compilation of such unusual stereochemical effects and initial evaluation of the nature of the force field inside nanotubes and fullerenes.

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Section: 3-dioxane In Nanotubesmentioning

confidence: 99%