Logo image
Back
Copper(II) complexes of tetradentate thioether-oxime ligands
Journal article   Peer reviewed

Copper(II) complexes of tetradentate thioether-oxime ligands

Michael J. Prushan, Anthony W. Addison, Raymond J. Butcher and Laurence K. Thompson
Inorganica Chimica Acta, v 358(12), pp 3449-3456
2005
DOI: https://doi.org/10.1016/j.ica.2005.04.038
Featured in Collection :   UN Sustainable Development Goals @ Drexel

Abstract

Copper Crystal structure Electrochemistry Magnetochemistry Thioether-oxime
Two dinuclear copper(II) thioether-oxime complexes were synthesized. Macrocyclization of [Cu(DtdoH)] 2(ClO 4) 2 with BF 2 + yielded the monomer [Cu(Thyclops)]ClO 4. The complexes were characterized by X-ray crystallography, UV–visible and ESR spectrometry. Electrochemical measurements indicate that this class of ligands stabilizes copper(II). The dinuclear complexes were additionally characterized by VT magnetometry. Very weak ferromagnetic exchange is the dominating interaction in the dinuclear complexes. Two dinuclear copper(II) thioether-oxime complexes ([Cu(DtdoH)] 2(ClO 4) 2 and [Cu(DtudH)] 2(ClO 4) 2 · 2CH 3OH) have been synthesized. [Cu(DtdoH)] 2(ClO 4) 2 reacted with excess BF 3 · OEt 2 to yield [Cu(Thyclops)]ClO 4, a BF 2 + -macrocyclized di-oxime. [Cu(DtdoH)] 2(ClO 4) 2 and [Cu(DtudH)] 2(ClO 4) 2 · 2CH 3OH are the first representatives of copper(II) thioether oximes which exhibit the classical out-of-plane oximate oxygen-metal dimer structure. [Cu(DtdoH)] 2(ClO 4) 2 and [Cu(Thyclops)]ClO 4 have been structurally characterized by single-crystal X-ray diffraction. The geometry about each copper(II) in [Cu(DtdoH)] 2(ClO 4) 2 is a distorted square pyramid ( τ = 0.14). The average copper–nitrogen(oxime) bond length is 1.984 Å longer (∼0.03 Å) than the average copper–nitrogen(oxime) bonds in copper(II) bis-glyoximates. The geometry of [Cu(Thyclops)]ClO 4 reveals an almost perfect square pyramid ( τ = 0.03) of N 2S 2O donors. Solution, cryogenic glass, and powder ESR spectra show a typical axial pattern, except for the powder spectrum of [Cu(DtudH)] 2(ClO 4) 2 · 2CH 3OH which displays a small rhombic distortion. Variable-temperature magnetic susceptibility measurements indicate very weak ferromagnetic interactions in [Cu(DtdoH)] 2(ClO 4) 2, where J = +0.52 cm −1 and very weak antiferromagnetic interactions in [Cu(DtudH)] 2(ClO 4) 2 · 2CH 3OH, where J = −0.59 cm −1. Electrochemical measurements reveal that the mixed thioether-oxime coordination environment tends to stabilize Cu(II), as all electrochemical reductions were quasi-reversible or irreversible. [Cu(Thyclops)]ClO 4 is more oxidizing than [Cu(DtdoH)] 2(ClO 4) 2 by 0.14 V.

Metrics

3 Record Views
37 citations in Web of Science
39 citations in Scopus

Details

UN Sustainable Development Goals (SDGs)

This publication has contributed to the advancement of the following goals:

#3 Good Health and Well-Being

InCites Highlights

Data related to this publication, from InCites Benchmarking & Analytics tool:

Collaboration types
Domestic collaboration
International collaboration
Web of Science research areas
Chemistry, Inorganic & Nuclear
Logo image