title: Molecular and crystal structures of 2-phenyl-2-hydro-6-methyl-1,3-dioxa-6-aza-2-silacyclooctane
metadata.name: dc.contributor.author
metadata.value: Ignatyev, I.S.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Kochina, T.A.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Avronin, V.V.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Gurzhiy, Vladislav V.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Fundamensky, V.S.
metadata.lang: -
metadata.name: dc.date.accessioned
metadata.value: 2016-05-06T13:09:24Z
metadata.lang: -
metadata.name: dc.date.available
metadata.value: 2016-05-06T13:09:24Z
metadata.lang: -
metadata.name: dc.date.issued
metadata.value: 2015-08
metadata.lang: -
metadata.name: dc.identifier.issn
metadata.value: 0022-2860
metadata.lang: -
metadata.name: dc.identifier.other
metadata.value: 10.1016/j.molstruc.2015.03.061
metadata.lang: -
metadata.name: dc.identifier.uri
metadata.value: http://hdl.handle.net/11701/2245
metadata.lang: -
metadata.name: dc.description.abstract
metadata.value: The crystal structure of 2-phenyl-2-hydro-6-methyl-1,3-dioxa-6-aza-2-silacyclooctane [HPhSi(OCH2CH2)2NMe – phenylhydrosilocane (I)] is determined by single-crystal X-ray diffraction at 100 K. The unit cell consists of four molecules connected only by Van-der-Waals interactions. Each molecule has an eight-membered heterocycle with a phenyl group in the axial position. The Si⋯N transannular bond has a short (2.206 Å) interatomic distance which exceeds only this distance in ocanes with highly electronegative fluorine substituents at Si. Since there exist experimental data on the occurrence of different conformers of I in the liquid phase, the PES of the molecule was analyzed by DFT B3LYP and MP2 methods with the aug-cc-pVDZ basis set. The energy minimum belongs to the boat–chair conformation with the axial position of the phenyl group. Rotation of the phenyl ring around the SiC bond has a barrier ca. 1 kcal/mol. The conformer with the equatorial position of this group lies 6 kcal/mol higher. Interconversion of this conformers which was observed in experiment proceeds through the chair–chair configuration in which the Si⋯N transannular bond is absent and coordination at silicon is tetrahedral, rather than trigonal bipyramidal one observed in other conformers.
metadata.lang: en_GB
metadata.name: dc.language.iso
metadata.value: en
metadata.lang: en_GB
metadata.name: dc.publisher
metadata.value: Elsevier
metadata.lang: en_GB
metadata.name: dc.relation.ispartofseries
metadata.value: Journal of Molecular Structure;V. 1094
metadata.lang: -
metadata.name: dc.subject
metadata.value: Pentacoordinate silicon
metadata.lang: en_GB
metadata.name: dc.subject
metadata.value: Silocanes
metadata.lang: en_GB
metadata.name: dc.subject
metadata.value: Quasisilatranes
metadata.lang: en_GB
metadata.name: dc.subject
metadata.value: DFT
metadata.lang: en_GB
metadata.name: dc.subject
metadata.value: Conformers
metadata.lang: en_GB
metadata.name: dc.subject
metadata.value: X-ray diffraction
metadata.lang: en_GB
metadata.name: dc.title
metadata.value: Molecular and crystal structures of 2-phenyl-2-hydro-6-methyl-1,3-dioxa-6-aza-2-silacyclooctane
metadata.lang: en_GB
metadata.name: dc.type
metadata.value: Article
metadata.lang: en_GB
resources.filename: 2015_VSF_J MolecStr.pdf
resources.url: https://dspace.spbu.ru/bitstream/11701/2245/1/2015_VSF_J%20MolecStr.pdf
resources.format: Adobe PDF
resources.size: 683,31 kB