Influence of the steric demand of the 2,4,6-trialkylphenyl substituents on the structures and reactivity of diarylzinc

Matthias Westerhausen, Manfred W. Oßberger, Jacob S. Alexander, Karin Ruhlandt

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The Grignard reaction of 2,4,6-tri(tert-butyl)phenylmagnesium bromide with zinc dichloride in THF yields monomeric bis[2,4,6-tri(tert-butyl)phenyl]zinc (1). Due to the steric demand of the tert-butyl groups 1 has a bent CZnC moiety and the boat-shaped aryl groups are in a staggered conformation. After the transmetallation of 1 with cesium in a solvent mixture of 1,2-dimethoxyethane (DME) and toluene (1,2-dimethoxyethane-O,O′)cesium [2,4,6-tri(tert-butyl) phenolate] (2) is isolated. A polymeric structure is formed in the crystalline state by linkage of these molecules via a Cs-O bond of the phenolate oxygen atoms and a η6-coordination of the aryl moiety of another molecule to the cesium cations. Furthermore, in the solid state the cesium cation completes his coordination sphere by bonds to a bidentate ether molecule and by close contacts to a tert-butyl group of a neighboring molecule.

Original languageEnglish (US)
Pages (from-to)2836-2841
Number of pages6
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume631
Issue number13-14
DOIs
StatePublished - 2005

Fingerprint

Cesium
Molecules
Cations
Zinc
Toluene
Boats
Bromides
Ether
Conformations
Oxygen
Crystalline materials
Atoms
1,2-dimethoxyethane

Keywords

  • Cesium
  • Diarylzinc
  • Grignard Reactions
  • Transmetallation Reactions
  • Zinc

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Influence of the steric demand of the 2,4,6-trialkylphenyl substituents on the structures and reactivity of diarylzinc. / Westerhausen, Matthias; Oßberger, Manfred W.; Alexander, Jacob S.; Ruhlandt, Karin.

In: Zeitschrift fur Anorganische und Allgemeine Chemie, Vol. 631, No. 13-14, 2005, p. 2836-2841.

Research output: Contribution to journalArticle

@article{b68b46a21b434250b73096bc3b8018b0,
title = "Influence of the steric demand of the 2,4,6-trialkylphenyl substituents on the structures and reactivity of diarylzinc",
abstract = "The Grignard reaction of 2,4,6-tri(tert-butyl)phenylmagnesium bromide with zinc dichloride in THF yields monomeric bis[2,4,6-tri(tert-butyl)phenyl]zinc (1). Due to the steric demand of the tert-butyl groups 1 has a bent CZnC moiety and the boat-shaped aryl groups are in a staggered conformation. After the transmetallation of 1 with cesium in a solvent mixture of 1,2-dimethoxyethane (DME) and toluene (1,2-dimethoxyethane-O,O′)cesium [2,4,6-tri(tert-butyl) phenolate] (2) is isolated. A polymeric structure is formed in the crystalline state by linkage of these molecules via a Cs-O bond of the phenolate oxygen atoms and a η6-coordination of the aryl moiety of another molecule to the cesium cations. Furthermore, in the solid state the cesium cation completes his coordination sphere by bonds to a bidentate ether molecule and by close contacts to a tert-butyl group of a neighboring molecule.",
keywords = "Cesium, Diarylzinc, Grignard Reactions, Transmetallation Reactions, Zinc",
author = "Matthias Westerhausen and O{\ss}berger, {Manfred W.} and Alexander, {Jacob S.} and Karin Ruhlandt",
year = "2005",
doi = "10.1002/zaac.200500165",
language = "English (US)",
volume = "631",
pages = "2836--2841",
journal = "Zeitschrift fur Anorganische und Allgemeine Chemie",
issn = "0044-2313",
publisher = "Wiley-VCH Verlag",
number = "13-14",

}

TY - JOUR

T1 - Influence of the steric demand of the 2,4,6-trialkylphenyl substituents on the structures and reactivity of diarylzinc

AU - Westerhausen, Matthias

AU - Oßberger, Manfred W.

AU - Alexander, Jacob S.

AU - Ruhlandt, Karin

PY - 2005

Y1 - 2005

N2 - The Grignard reaction of 2,4,6-tri(tert-butyl)phenylmagnesium bromide with zinc dichloride in THF yields monomeric bis[2,4,6-tri(tert-butyl)phenyl]zinc (1). Due to the steric demand of the tert-butyl groups 1 has a bent CZnC moiety and the boat-shaped aryl groups are in a staggered conformation. After the transmetallation of 1 with cesium in a solvent mixture of 1,2-dimethoxyethane (DME) and toluene (1,2-dimethoxyethane-O,O′)cesium [2,4,6-tri(tert-butyl) phenolate] (2) is isolated. A polymeric structure is formed in the crystalline state by linkage of these molecules via a Cs-O bond of the phenolate oxygen atoms and a η6-coordination of the aryl moiety of another molecule to the cesium cations. Furthermore, in the solid state the cesium cation completes his coordination sphere by bonds to a bidentate ether molecule and by close contacts to a tert-butyl group of a neighboring molecule.

AB - The Grignard reaction of 2,4,6-tri(tert-butyl)phenylmagnesium bromide with zinc dichloride in THF yields monomeric bis[2,4,6-tri(tert-butyl)phenyl]zinc (1). Due to the steric demand of the tert-butyl groups 1 has a bent CZnC moiety and the boat-shaped aryl groups are in a staggered conformation. After the transmetallation of 1 with cesium in a solvent mixture of 1,2-dimethoxyethane (DME) and toluene (1,2-dimethoxyethane-O,O′)cesium [2,4,6-tri(tert-butyl) phenolate] (2) is isolated. A polymeric structure is formed in the crystalline state by linkage of these molecules via a Cs-O bond of the phenolate oxygen atoms and a η6-coordination of the aryl moiety of another molecule to the cesium cations. Furthermore, in the solid state the cesium cation completes his coordination sphere by bonds to a bidentate ether molecule and by close contacts to a tert-butyl group of a neighboring molecule.

KW - Cesium

KW - Diarylzinc

KW - Grignard Reactions

KW - Transmetallation Reactions

KW - Zinc

UR - http://www.scopus.com/inward/record.url?scp=27644515977&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=27644515977&partnerID=8YFLogxK

U2 - 10.1002/zaac.200500165

DO - 10.1002/zaac.200500165

M3 - Article

VL - 631

SP - 2836

EP - 2841

JO - Zeitschrift fur Anorganische und Allgemeine Chemie

JF - Zeitschrift fur Anorganische und Allgemeine Chemie

SN - 0044-2313

IS - 13-14

ER -