Issue 10, 2007
From the journal:

New Journal of Chemistry

A combined spectroscopic and theoretical approach to investigate structural properties of Co(ii)/Co(iii) tris-cysteinato complexes in aqueous medium†

Carole Bresson,*a   Riccardo Spezia,*b   Stéphane Esnouf,c   Pier Lorenzo Solari,d   Stéphanie Coantice  and  Christophe Den Auwerf  

* Corresponding authors

a CEA Saclay, DEN/DPC/SECR/LSRM, France
E-mail: carole.bresson@cea.fr
Fax: +33 1 690 854 11
Tel: +33 1 690 883 48

b LAMBE, UMR CNRS 8587, Université d’Evry-Val-d’Essonne, France
E-mail: riccardo.spezia@univ-evry.fr
Fax: +33 1 694 776 55
Tel: +33 1 694 776 53

c Ecole Polytechnique, DSM/DRECAM/LSI, France

d Synchrotron Soleil, Saint Aubin - BP 48, France

e ICSM, FRE CEA/CNRS 2926, CEA Valrhô/DRCP/SCPS/LCAM, BP 17171, France

f CEA Marcoule, DEN/DRCP/SCPS, France

Abstract

Physiological and toxicological effects of metallic ions depend on their speciation and on the structure of their associated bioligand complexes. In the field of chemical and/or nuclear toxicological studies, we are investigating cobalt complexes with biorelevant ligands such as amino acids or peptides. The aqueous reaction of cobalt dichloride with an excess of cysteine (Cys, C3H5NSO22−) in a basic medium under an anaerobic atmosphere and subsequent oxidation by O2, afforded the mononuclear complexes Co(II):3Cys and Co(III):3Cys, respectively. A combination of X-ray absorption spectroscopy (XAS) measurements and Car-Parrinello molecular dynamics (CPMD) simulations allowed us to assess structural features of the already explored Co(III):3Cys complex. Inclusion of the temperature effects in the CPMD calculations gives an implicit access to disorder effects in the extended X-ray absorption fine structure (EXAFS) equation. The very good agreement between the measured and the simulated data showed the accuracy of these models provided by CPMD. The present investigation is completed by new UV-visible, X-ray absorption near edge structure (XANES) and electron paramagnetic resonance (EPR) data of Co(II):3Cys. These data are consistent with a Co(II) high-spin d7 complex in a distorted octahedral geometry. This work contributes to the knowledge of topics such as metal–bioligand interaction which is of major interest in the field of bioinorganic chemistry.

Graphical abstract: A combined spectroscopic and theoretical approach to investigate structural properties of Co(ii)/Co(iii) tris-cysteinato complexes in aqueous medium

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Article information

DOI
https://doi.org/10.1039/B707055A
Article type
Paper
Submitted
09 May 2007
Accepted
11 Jun 2007
First published
28 Jun 2007

New J. Chem., 2007,31, 1789-1797

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A combined spectroscopic and theoretical approach to investigate structural properties of Co(II)/Co(III) tris-cysteinato complexes in aqueous medium

C. Bresson, R. Spezia, S. Esnouf, P. L. Solari, S. Coantic and C. Den Auwer, New J. Chem., 2007, 31, 1789 DOI: 10.1039/B707055A

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