Please use this identifier to cite or link to this item:
Main Title: Tetrahalidocuprates(II)-structure and EPR spectroscopy. Part 1: Tetrabromidocuprates(II)
Author(s): Farra, Ramzi
Thiel, Kerstin
Winter, Alette
Klamroth, Tillmann
Pöppl, Andreas
Kelling, Alexandra
Schilde, Uwe
Taubert, Andreas
Strauch, Peter
Type: Article
Language Code: en
Abstract: Tetrahalidocuprates(II) show a high degree of structural flexibility. We present the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of four new tetrabromidocuprate(II) compounds and compare the results with previously reported data. The cations in the new compounds are the sterically demanding benzyltriphenylphosphonium, methyltriphenylphosphonium, tetraphenylphosphonium, and hexadecyltrimethylammonium ions; they were used to achieve a reasonable separation of the paramagnetic Cu(II) ions for EPR spectroscopy. X-Ray crystallography shows that in all four complexes the [CuBr4]2− units have a distorted tetrahedral coordination geometry which is in agreement with DFT calculations. The EPR hyperfine structure was not resolved. This is due to the exchange broadening resulting from still incomplete separation of the paramagnetic Cu(II) centres. Nevertheless, the principal values of the electron Zeemann tensor (g
and g⊥) of the complexes could be determined. A correlation of structural (X-ray) parameters with the spin density at the copper centres (DFT) is well reflected in the EPR spectra of the bromidocuprates. This enables the correlation of X-ray and EPR parameters to predict the structure of tetrabromidocuprates in physical states other than the crystalline state. As a result, we provide a method to structurally characterize [CuBr4]2− in, for example, ionic liquids or in solution, which has important implications for e.g. catalysis or materials science.
Issue Date: 2011
Date Available: 29-Jun-2016
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Journal Title: New journal of chemistry
Publisher: Royal Society of Chemistry
Publisher Place: Cambridge
Volume: 35
Issue: 12
Publisher DOI: 10.1039/c1nj20271e
Page Start: 2793
Page End: 2803
EISSN: 1144-0546
Notes: Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.
Appears in Collections:Inst. Chemie » Publications

Files in This Item:
File Description SizeFormat 
c1nj20271e.pdf2.31 MBAdobe PDFThumbnail

Items in DepositOnce are protected by copyright, with all rights reserved, unless otherwise indicated.