Oxido-pincer complexes of copper(II) – An EXAFS and EPR study of mono- and binuclear [(pydotH[sub]2)CuCl[sub]2][sub]n (n = 1 or 2)

Klein, Axel, Butsch, Katharina, Elmas, Sait, Biewer, Christian, Heift, Dominikus, Nitsche, Sara, Schlipf, Irene and Bertagnoli, Helmut (2012) Oxido-pincer complexes of copper(II) – An EXAFS and EPR study of mono- and binuclear [(pydotH[sub]2)CuCl[sub]2][sub]n (n = 1 or 2). Polyhedron, 31(1), pp. 649-656. ISSN (print) 0277-5387

Official URL: https://doi.org/10.1016/j.poly.2011.10.023

Abstract

The oxido-pincer ligand pydotH2 (2,6-bis(1-hydroxy-1-o-tolyl-ethyl-η2O,O′)pyridine) forms two different CuII containing complexes when prepared from anhydrous CuCl2. A combination of EPR spectroscopy and EXAFS allowed to structurally characterise the light-green dimer of the formula [(pydotH2)CuCl(μ-Cl)2ClCu(pydotH2)] and the penta-coordinate olive-green monomer [(pydotH2)CuCl2]. The molecular entities imply that the ligand remains protonated upon coordination. When dissolved in DMF both compounds form monomeric species [(pydotH2)CuCl2(DMF)] which could be characterised in detail by EPR, UV–Vis/NIR spectroscopy and electrochemical measurements. The assignments were supported by comparison with CuII complexes of the related ligands 2,6-bis(hydroxymethyl)pyridine (pydimH2) and 2,6-bis(1-hydroxy-1-methyl)pyridine (pydipH2).

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