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Influence of the Steric Demand of the 2,4,6‐Trialkylphenyl Substituents on the Structures and Reactivity of Diarylzinc
Author(s) -
Westerhausen Matthias,
Oßberger Manfred W.,
Alexander Jacob S.,
RuhlandtSenge Karin
Publication year - 2005
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200500165
Subject(s) - chemistry , steric effects , moiety , molecule , dimethoxyethane , medicinal chemistry , aryl , denticity , reactivity (psychology) , coordination sphere , monomer , bromide , transmetalation , ether , supramolecular chemistry , stereochemistry , polymer chemistry , crystal structure , crystallography , organic chemistry , medicine , alkyl , alternative medicine , electrode , pathology , electrolyte , polymer , catalysis
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 η 6 ‐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.