Oxido-pincer complexes of copper (II): an EXAFS and EPR study of mono- and binuclear [(pydotH2) CuCl2] n (n= 1 or 2)

Axel Klein; Katharina Butsch; Sait Elmas; Christian Biewer; Dominikus Heift; Sara Nitsche; Irene Schlipf; Helmut Bertagnolli

doi:10.1016/j.poly.2011.10.023

Oxido-pincer complexes of copper (II): an EXAFS and EPR study of mono- and binuclear [(pydotH2) CuCl2] n (n= 1 or 2)

Axel Klein, Katharina Butsch, Sait Elmas, Christian Biewer, Dominikus Heift, Sara Nitsche, Irene Schlipf, Helmut Bertagnolli

Flinders Institute for Nanoscale Science and Technology

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

Abstract

The oxido-pincer ligand pydotH₂ (2,6-bis(1-hydroxy-1-o-tolyl- ethyl-η²O,O′)pyridine) forms two different Cu^II 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 Cu^II complexes of the related ligands 2,6-bis(hydroxymethyl)pyridine (pydimH₂) and 2,6-bis(1-hydroxy-1-methyl)pyridine (pydipH ₂).

Original language	English
Pages (from-to)	649-656
Number of pages	8
Journal	POLYHEDRON
Volume	31
Issue number	1
DOIs	https://doi.org/10.1016/j.poly.2011.10.023
Publication status	Published - 4 Jan 2012

Keywords

oxido-pincer ligand
copper
EPR spectroscopy
coordination geometry

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@article{ffbee26227f2402f889c38a81424168d,

title = "Oxido-pincer complexes of copper (II): an EXAFS and EPR study of mono- and binuclear [(pydotH2) CuCl2] n (n= 1 or 2)",

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 (pydipH 2).",

keywords = "oxido-pincer ligand, copper, EPR spectroscopy, coordination geometry",

author = "Axel Klein and Katharina Butsch and Sait Elmas and Christian Biewer and Dominikus Heift and Sara Nitsche and Irene Schlipf and Helmut Bertagnolli",

year = "2012",

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doi = "10.1016/j.poly.2011.10.023",

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T1 - Oxido-pincer complexes of copper (II)

T2 - an EXAFS and EPR study of mono- and binuclear [(pydotH2) CuCl2] n (n= 1 or 2)

AU - Klein, Axel

AU - Butsch, Katharina

AU - Elmas, Sait

AU - Biewer, Christian

AU - Heift, Dominikus

AU - Nitsche, Sara

AU - Schlipf, Irene

AU - Bertagnolli, Helmut

PY - 2012/1/4

Y1 - 2012/1/4

N2 - 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 (pydipH 2).

AB - 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 (pydipH 2).

KW - oxido-pincer ligand

KW - copper

KW - EPR spectroscopy

KW - coordination geometry

U2 - 10.1016/j.poly.2011.10.023

DO - 10.1016/j.poly.2011.10.023

M3 - Article

SN - 0277-5387

VL - 31

SP - 649

EP - 656

JO - POLYHEDRON

JF - POLYHEDRON

IS - 1

ER -

Oxido-pincer complexes of copper (II): an EXAFS and EPR study of mono- and binuclear [(pydotH2) CuCl2] n (n= 1 or 2)

Abstract

Keywords

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