X-ray Absorption Spectra of CuII and CuIII Complexes of N,N′-1,2-Phenylenebis(2-mercapto-2-methylpropionamide)

✍ Scribed by Giampaolo Barone; Gianfranco La Manna; Dario Duca

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: English
• Weight: 146 KB
• Volume: 2005
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200400495

✦ Synopsis

Abstract

The X‐ray absorption spectra of Cu^II^ and Cu^III^ complexes of N,N′‐1,2‐phenylenebis(2‐mercapto‐2‐methylpropionamide) were recorded and analysed in solid phase. The EXAFS spectra of the two samples were refined with full multiple scattering path. Geometry optimisations on the Cu^II^ and Cu^III^ complexes were performed by the B3LYP density functional method, with the 6‐31G(d,p) basis set, considering different spin multiplicities. The singlet state of the Cu^III^ complex was shown to be more stable than the triplet state, and a good agreement between the calculated and the corresponding experimental structure was found. Further single‐point calculations on the optimised geometry were carried out at the Hartree−Fock level for obtaining molecular orbital eigenvectors and eigenvalues. The latter were employed as parameters in a new fitting approach to rationalise the shape of the K‐edge of the XAS spectra. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)