The experimental gas-phase structures of 1,3,5-trisilylbenzene and hexasilylbenzene and the theoretical structures of all benzenes with three or more silyl substituents

B. Johnston, N.W. Mitzel, D.W.H. Rankin, H.E. Robertson, C. Rüdinger, H. Schmidbaur

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The structures of 1,3,5-trisilylbenzene and hexasilylbenzene in the gas phase have been determined by electron diffraction, and that of 1,3,5-trisilylbenzene by X-ray crystallography. The structures of three trisilylbenzene isomers, three tetrasilylbenzenes, pentasilylbenzene and hexasilylbenzene have been computed, ab initio and using Density Functional Theory, at levels up to MP2/6-31G*. The primary effect of silyl substituents is to narrow the ring angle at the substituted carbon atoms. Steric interactions between silyl groups on neighbouring carbon atoms lead first to displacement of these groups away from one another, and then to displacement out of the ring plane, with alternate groups moving to opposite sides of the ring. In the extreme example, hexasilylbenzene, the SiCCSi dihedral angle is 17.8(8)°.



LanguageEnglish
Pages2292-2299
Number of pages8
JournalDalton Transactions
Volume13
DOIs
Publication statusPublished - 2005

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Phase structure
Benzene
Carbon
Gases
Atoms
X ray crystallography
Dihedral angle
Electron diffraction
Isomers
Density functional theory

Keywords

  • Crystal structure data
  • X-ray crystallography

Cite this

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title = "The experimental gas-phase structures of 1,3,5-trisilylbenzene and hexasilylbenzene and the theoretical structures of all benzenes with three or more silyl substituents",
abstract = "The structures of 1,3,5-trisilylbenzene and hexasilylbenzene in the gas phase have been determined by electron diffraction, and that of 1,3,5-trisilylbenzene by X-ray crystallography. The structures of three trisilylbenzene isomers, three tetrasilylbenzenes, pentasilylbenzene and hexasilylbenzene have been computed, ab initio and using Density Functional Theory, at levels up to MP2/6-31G*. The primary effect of silyl substituents is to narrow the ring angle at the substituted carbon atoms. Steric interactions between silyl groups on neighbouring carbon atoms lead first to displacement of these groups away from one another, and then to displacement out of the ring plane, with alternate groups moving to opposite sides of the ring. In the extreme example, hexasilylbenzene, the SiCCSi dihedral angle is 17.8(8)°.",
keywords = "Crystal structure data , X-ray crystallography",
author = "B. Johnston and N.W. Mitzel and D.W.H. Rankin and H.E. Robertson and C. R{\"u}dinger and H. Schmidbaur",
year = "2005",
doi = "10.1039/b503637b",
language = "English",
volume = "13",
pages = "2292--2299",
journal = "Dalton Transactions",
issn = "1477-9226",

}

The experimental gas-phase structures of 1,3,5-trisilylbenzene and hexasilylbenzene and the theoretical structures of all benzenes with three or more silyl substituents. / Johnston, B.; Mitzel, N.W.; Rankin, D.W.H.; Robertson, H.E.; Rüdinger, C.; Schmidbaur, H.

In: Dalton Transactions, Vol. 13, 2005, p. 2292-2299.

Research output: Contribution to journalArticle

TY - JOUR

T1 - The experimental gas-phase structures of 1,3,5-trisilylbenzene and hexasilylbenzene and the theoretical structures of all benzenes with three or more silyl substituents

AU - Johnston, B.

AU - Mitzel, N.W.

AU - Rankin, D.W.H.

AU - Robertson, H.E.

AU - Rüdinger, C.

AU - Schmidbaur, H.

PY - 2005

Y1 - 2005

N2 - The structures of 1,3,5-trisilylbenzene and hexasilylbenzene in the gas phase have been determined by electron diffraction, and that of 1,3,5-trisilylbenzene by X-ray crystallography. The structures of three trisilylbenzene isomers, three tetrasilylbenzenes, pentasilylbenzene and hexasilylbenzene have been computed, ab initio and using Density Functional Theory, at levels up to MP2/6-31G*. The primary effect of silyl substituents is to narrow the ring angle at the substituted carbon atoms. Steric interactions between silyl groups on neighbouring carbon atoms lead first to displacement of these groups away from one another, and then to displacement out of the ring plane, with alternate groups moving to opposite sides of the ring. In the extreme example, hexasilylbenzene, the SiCCSi dihedral angle is 17.8(8)°.

AB - The structures of 1,3,5-trisilylbenzene and hexasilylbenzene in the gas phase have been determined by electron diffraction, and that of 1,3,5-trisilylbenzene by X-ray crystallography. The structures of three trisilylbenzene isomers, three tetrasilylbenzenes, pentasilylbenzene and hexasilylbenzene have been computed, ab initio and using Density Functional Theory, at levels up to MP2/6-31G*. The primary effect of silyl substituents is to narrow the ring angle at the substituted carbon atoms. Steric interactions between silyl groups on neighbouring carbon atoms lead first to displacement of these groups away from one another, and then to displacement out of the ring plane, with alternate groups moving to opposite sides of the ring. In the extreme example, hexasilylbenzene, the SiCCSi dihedral angle is 17.8(8)°.

KW - Crystal structure data

KW - X-ray crystallography

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