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Type: Journal article
Title: Structural and spectroscopic studies of halocuprate(I) and haloargentate(I) complexes [M₂XnX '₄-n]²⁻
Other Titles: Structural and spectroscopic studies of halocuprate(I) and haloargentate(I) complexes [M(2)XnX'(4)-n](2-)
Author: Bowmaker, G.
Bruce, M.
Skelton, B.
Somers, N.
White, A.
Citation: Zeitschrift fuer Anorganische und Allgemeine Chemie, 2007; 633(7):1024-1030
Publisher: Wiley-V C H Verlag GMBH
Issue Date: 2007
ISSN: 0044-2313
Statement of
Graham A. Bowmaker, Michael I. Bruce, Brian W. Skelton, Neil Somers, Allan H. White
Abstract: <jats:title>Abstract</jats:title><jats:p>The complexes [Cu<jats:sub>2</jats:sub>Br<jats:sub>4</jats:sub>]<jats:sup>2−</jats:sup>, [Cu<jats:sub>2</jats:sub>I<jats:sub>4</jats:sub>]<jats:sup>2−</jats:sup>, [Cu<jats:sub>2</jats:sub>I<jats:sub>2</jats:sub>Br<jats:sub>2</jats:sub>]<jats:sup>2−</jats:sup>, [Cu<jats:sub>2</jats:sub>I<jats:sub>3</jats:sub>Cl]<jats:sup>2−</jats:sup>, [Ag<jats:sub>2</jats:sub>Cl<jats:sub>4</jats:sub>]<jats:sup>2−</jats:sup> have been characterized as their isomorphous bis(triphenylphosphoranylidene)ammonium ([Ph<jats:sub>3</jats:sub>PNPPh<jats:sub>3</jats:sub>]<jats:sup>+</jats:sup> = PNP<jats:sup>+</jats:sup>) salts by single crystal structural determinations. All anions show the centrosymmetric doubly halogen‐bridged forms [XM(μ‐X)<jats:sub>2</jats:sub>MX]<jats:sup>2−</jats:sup> with three‐coordinate metal atoms that have been observed in [M<jats:sub>2</jats:sub>X<jats:sub>4</jats:sub>]<jats:sup>2−</jats:sup> complexes with other large organic cations. In [Cu<jats:sub>2</jats:sub>I<jats:sub>2</jats:sub>Br<jats:sub>2</jats:sub>]<jats:sup>2−</jats:sup> the iodide ligands occupy the bridging positions and the bromide the terminal positions, while in [Cu<jats:sub>2</jats:sub>I<jats:sub>3</jats:sub>Cl]<jats:sup>2−</jats:sup>, obtained in an attempt to prepare [Cu<jats:sub>2</jats:sub>I<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub>]<jats:sup>2−</jats:sup>, two of the iodide ligands occupy the bridging positions with the third iodide and the chloride ligand occupying two statistically disordered terminal positions. In [Ag<jats:sub>2</jats:sub>Cl<jats:sub>4</jats:sub>]<jats:sup>2−</jats:sup> the distortion from ideal trigonal coordination of the metal atom is greater than in the copper complexes, but less than in other previously reported [Ag<jats:sub>2</jats:sub>Cl<jats:sub>4</jats:sub>]<jats:sup>2−</jats:sup> complexes with organic cations. The ν(MX) bands have been assigned in the far‐IR spectra, and confirm previous observations regarding the unexpectedly simple IR spectra of [Cu<jats:sub>2</jats:sub>X<jats:sub>4</jats:sub>]<jats:sup>2−</jats:sup> complexes.</jats:p>
Description: Copyright © 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Provenance: Published Online: 23 Apr 2007
DOI: 10.1002/zaac.200700051
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