Spectrochemical and Electrochemical Properties of Distorted Pentacoordinate [Cu(chel)2X]Y Complexes

Ondrejovič, G., Kotočová, A. and Valigura, D. Spectrochemical and Electrochemical Properties of Distorted Pentacoordinate [Cu(chel)2X]Y Complexes Chemical Papers, Vol.56, No. 3, 2002, 168-173

Document type: Článok z časopisu / Journal Article
Collection: Chemical papers  
 
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Author(s) Ondrejovič, G.
Kotočová, A.
Valigura, D.
Title Spectrochemical and Electrochemical Properties of Distorted Pentacoordinate [Cu(chel)2X]Y Complexes
Journal name Chemical Papers
Publication date 2002
Year available 2002
Volume number 56
Issue number 3
ISSN 0366-6352
Start page 168
End page 173
Place of publication Poland
Publisher Versita
Collection year 2002
Language english
Subject 250000 Chemical Sciences
250200 Inorganic Chemistry
Abstract/Summary The trigonal bipyramidal complexes of the general formula [Cu(chel)2X]ClO4, where chel = 2,2- bipyridine (bpy), 1,10-phenanthroline (phen); X = Cl−, Br−, I−, NCS−, CN−, were prepared and their electronic absorption spectra were measured in Nujol mull and nitromethane solution. Using Hathaway’s electronic criteria the square-based pyramidal distortion of the trigonal bipyramidal coordination of the complexes in the solid state as well as in nitromethane solutions was analyzed. The electronic spectra indicate that the solid bpy complexes are more distorted than their phen analogues, the greatest difference being found for chloro and the smallest for isothiocyanato complexes. The electronic spectra of some complexes in nitromethane indicate square-based pyramidal distorted trigonal bipyramidal coordinations, while another indicate near trigonal bipyramidal coordinations. The halfwave potentials of complexes in nitromethane, except cyano complexes were in the range −0.40 V— −0.32 V for bpy and −0.43 V— −0.34 V for phen complexes vs. ferrocenium/ferrocene couple. A linear correlation between the halfwave potentials and the standard electrode potentials Eº(X2/X−) was found for both series of bpy and phen [Cu(chel)2X]ClO4 complexes in nitromethane indicating that the redox properties of the [Cu(chel)2X]ClO4 complexes are predominantly affected by the nature of the ligands X.
 
 
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