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Synthesis 2007(5): 725-730  
DOI: 10.1055/s-2007-965909
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Arylcalcium Halides - General Procedure, Scope and Limitations

Martin Gärtner, Helmar Görls, Matthias Westerhausen*
Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, August-Bebel-Str. 2, 07743 Jena, Germany
Fax: +49(3641)948110; e-Mail: m.we@uni-jena.de;
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Publication History

Received 16 November 2006
Publication Date:
25 January 2007 (online)

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Abstract

A general procedure for the synthesis of a wide variety of arylcalcium halides by activation of the alkaline earth metal as well as bromo- or iodoarenes is reported. Chloro- and fluoroarenes are not suitable substrates for an insertion of calcium into the carbon-halogen bond. Furthermore, ortho-fluoro substitution prevents the formation of the corresponding heavy calcium organometallics. The ipso-carbon atoms show a strong low-field shift in the 13C NMR spectra. The arylcalcium iodides crystallize monomeric as tetrakis(THF) complexes. Naphthylcalcium iodide shows a Ca-C bond length of 255.2(6) pm which lies in the characteristic region.

Keywords

Grignard reaction - arylcalcium halides - direct synthesis - calcium - metal activation

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CCDC-627216 contains the supplementary crystallographic data for compound 12. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336 033; or deposit@ccdc.cam.ac.uk).