Issue 2, 2011
From the journal:

Dalton Transactions

‘Double redox-activity’ in azobenzene-quinonoid palladium(ii) complexes: a combined structural, electrochemical and spectroscopic study†

Naina Deibel,a   David Schweinfurth,a   Ralph Huebner,a   Pierre Braunstein*b  and  Biprajit Sarkar*a  

* Corresponding authors

a Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, Stuttgart, Germany
E-mail: sarkar@iac.uni-stuttgart.de

b Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, Strasbourg Cedex, France
E-mail: braunstein@unistra.fr
Fax: (+)33368851322
Tel: (+)33368851308

Abstract

Reactions of [(az-H)Pd(μ-Cl)2Pd(az-H)] (az = azobenzene) with the zwitterionic, p-benzoquinonemonoimine-type ligands 4-(n-butylamino)-6(n-butylimino)-3-oxocyclohexa-1,4-dien-1-olate (Q1) or 4-(isopropylamino)-6(isopropylimino)-3-oxocyclohexa-1,4-dien-1-olate) (Q2) in the presence of a base leads to the formation of the mononuclear complexes [(az-H)Pd(Q1-H)] (1) and [(az-H)Pd(Q2-H)] (2) respectively. Structural characterization of 2 shows an almost square planar coordination geometry around the Pd(II) centre, a short Pd–C bond, a slight elongation of the N[double bond, length as m-dash]N double bond of the az-H ligand and localization of the double bonds within the Q2-H ligand. Additionally, intermolecular N–H–O interactions exist between the uncoordinated N–H and O groups of two different molecules. Cyclic voltammetry of the complexes reveals an irreversible oxidation and two reversible reduction processes. A combination of electrochemical and UV-vis-NIR and EPR spectroelectrochemical studies are used to show that both coordinated ligands participate successively in the redox processes, thus revealing their non-innocent character.

Graphical abstract: ‘Double redox-activity’ in azobenzene-quinonoid palladium(ii) complexes: a combined structural, electrochemical and spectroscopic study

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Article information

DOI
https://doi.org/10.1039/C0DT00944J
Article type
Paper
Submitted
02 Aug 2010
Accepted
12 Oct 2010
First published
26 Nov 2010

Dalton Trans., 2011,40, 431-436

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‘Double redox-activity’ in azobenzene-quinonoid palladium(II) complexes: a combined structural, electrochemical and spectroscopic study

N. Deibel, D. Schweinfurth, R. Huebner, P. Braunstein and B. Sarkar, Dalton Trans., 2011, 40, 431 DOI: 10.1039/C0DT00944J

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