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Title: Unusual two-dimensional sheet structure of the solvent-free cesium aryloxide complex CsO-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}

Abstract

During recent investigations into the structure and reactivity of lanthanide aryloxide derivatives, the authors have isolated a number of salt or ate complexes of the stoichiometry M{prime}[Ln(OAr){sub 4}] (M{prime} = K{sup 7}, Cs{sup 8}) and Cs{sub 2}[La(OAr){sub 5}]{sup 9} (Ar = 2,6-i-Pr{sub 2}C{sub 6}H{sub 3}) in which the coordination sphere of the alkali metal cations consists exclusively of multihapto {eta}-arene interactions with aryloxide ligands from adjacent [Ln(OAr){sub 4}]{sup {minus}} or [Ln(OAr){sub 5}]2{sup 2{minus}} units. Following preparation and utilization of the parent alkali metal aryloxide complex Cs(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}) during the synthesis of the lanthanum salts, the authors became aware of the dearth of structural data concerning heavy alkali metal aryloxide species. Although many complexes of both the lighter and heavier alkali metal aryloxides have been structurally characterized in which a crown ether is employed to encapsulate the cation, very few solvent-ligated or solvent-free aryloxide salts containing sodium, potassium, rubidium, or cesium have been subjected to X-ray diffraction studies. In the case of cesium, the authors have found only one example of a structurally characterized solvent-free aryloxide complex, namely cesium picrate Cs[O-2,4,6-(NO{sub 2}){sub 3}C{sub 6}H{sub 2}], which has been subjected to X-ray diffraction studies by two independent groups. In addition,more » very recent high-resolution powder X-ray diffraction data for cesium phenoxide (CsOPh) revealed a chain structure with both six-coordinate and three-coordinate metal ions and a very weak interaction between the cesium cation and an adjacent arene ring. Here, the authors report upon the unusual two-dimensional infinite-sheet structure of the solvent-free cesium aryloxide complex Cs(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}). To the best of their knowledge, this work represents the first structural characterization of an alkyl-substituted solvent-free aryloxide complex of the heavier alkali metals.« less

Authors:
; ; ; ;  [1]
  1. Los Alamos National Lab., NM (United States). Chemical Science and Technology Div.
Publication Date:
Sponsoring Org.:
USDOE, Washington, DC (United States)
OSTI Identifier:
321104
DOE Contract Number:  
W-7405-ENG-36
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 37; Journal Issue: 21; Other Information: PBD: 19 Oct 1998
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; CESIUM COMPOUNDS; PRASEODYMIUM COMPOUNDS; CRYSTAL STRUCTURE; ELECTRONIC STRUCTURE; ORGANOMETALLIC COMPOUNDS

Citation Formats

Clark, D L, Click, D R, Hollis, R V, Scott, B L, and Watkin, J G. Unusual two-dimensional sheet structure of the solvent-free cesium aryloxide complex CsO-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}. United States: N. p., 1998. Web. doi:10.1021/ic980630q.
Clark, D L, Click, D R, Hollis, R V, Scott, B L, & Watkin, J G. Unusual two-dimensional sheet structure of the solvent-free cesium aryloxide complex CsO-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}. United States. https://doi.org/10.1021/ic980630q
Clark, D L, Click, D R, Hollis, R V, Scott, B L, and Watkin, J G. Mon . "Unusual two-dimensional sheet structure of the solvent-free cesium aryloxide complex CsO-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}". United States. https://doi.org/10.1021/ic980630q.
@article{osti_321104,
title = {Unusual two-dimensional sheet structure of the solvent-free cesium aryloxide complex CsO-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}},
author = {Clark, D L and Click, D R and Hollis, R V and Scott, B L and Watkin, J G},
abstractNote = {During recent investigations into the structure and reactivity of lanthanide aryloxide derivatives, the authors have isolated a number of salt or ate complexes of the stoichiometry M{prime}[Ln(OAr){sub 4}] (M{prime} = K{sup 7}, Cs{sup 8}) and Cs{sub 2}[La(OAr){sub 5}]{sup 9} (Ar = 2,6-i-Pr{sub 2}C{sub 6}H{sub 3}) in which the coordination sphere of the alkali metal cations consists exclusively of multihapto {eta}-arene interactions with aryloxide ligands from adjacent [Ln(OAr){sub 4}]{sup {minus}} or [Ln(OAr){sub 5}]2{sup 2{minus}} units. Following preparation and utilization of the parent alkali metal aryloxide complex Cs(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}) during the synthesis of the lanthanum salts, the authors became aware of the dearth of structural data concerning heavy alkali metal aryloxide species. Although many complexes of both the lighter and heavier alkali metal aryloxides have been structurally characterized in which a crown ether is employed to encapsulate the cation, very few solvent-ligated or solvent-free aryloxide salts containing sodium, potassium, rubidium, or cesium have been subjected to X-ray diffraction studies. In the case of cesium, the authors have found only one example of a structurally characterized solvent-free aryloxide complex, namely cesium picrate Cs[O-2,4,6-(NO{sub 2}){sub 3}C{sub 6}H{sub 2}], which has been subjected to X-ray diffraction studies by two independent groups. In addition, very recent high-resolution powder X-ray diffraction data for cesium phenoxide (CsOPh) revealed a chain structure with both six-coordinate and three-coordinate metal ions and a very weak interaction between the cesium cation and an adjacent arene ring. Here, the authors report upon the unusual two-dimensional infinite-sheet structure of the solvent-free cesium aryloxide complex Cs(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}). To the best of their knowledge, this work represents the first structural characterization of an alkyl-substituted solvent-free aryloxide complex of the heavier alkali metals.},
doi = {10.1021/ic980630q},
url = {https://www.osti.gov/biblio/321104}, journal = {Inorganic Chemistry},
number = 21,
volume = 37,
place = {United States},
year = {1998},
month = {10}
}