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Issue 15, 2003
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Evaluation of the influence of a thioether substituent on the solid state and solution properties of N3S-ligated copper(II) complexes

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Abstract

Admixture of a N3S(thioether) ligand having two internal hydrogen bond donors (pbnpa: N-2-(phenylthio)ethyl-N,N-bis-((6-neopentylamino-2-pyridyl)methyl)amine; ebnpa: N-2-(ethylthio)ethyl-N,N-bis-((6-neopentylamino-2-pyridyl)methyl)amine) with equimolar amounts of Cu(ClO4)2·6H2O and NaX (X = Cl, NCO, or N3) in CH3OH/H2O yielded the mononuclear Cu(II) derivatives [(pbnpa)Cu–Cl]ClO4 (1), [(ebnpa)Cu–Cl]ClO4 (2), [(pbnpa)Cu–NCO]ClO4 (3), [(ebnpa)Cu–NCO]ClO4 (4), [(pbnpa)Cu–N3]ClO4 (5), and [(ebnpa)Cu–N3]ClO4 (6). Each complex was characterized by FTIR, UV-VIS, EPR, and elemental analysis. Complexes 1, 2, 3 and 6 were characterized by X-ray crystallography. The structural studies revealed that [(pbnpa)Cu–X]ClO4 derivatives (1, 3) exhibit a distorted square pyramidal type geometry, whereas [(ebnpa)Cu–X]ClO4 complexes (2, 6) may be classified as distorted trigonal bipyramidal. EPR studies in CH3OH/CH3CN solution revealed that 1–6 exhibit an axial type spectrum with g > g > 2.0 and A = 15–17 mT, consistent with a square pyramidal based geometry for the Cu(II) center in each complex. A second species detected in the EPR spectra of 2 and 6 has a smaller A value, consistent with greater spin delocalization on to sulfur, and likely results from geometric distortion of the [(ebnpa)Cu(II)–X]+ ions present in 2 and 6.

Graphical abstract: Evaluation of the influence of a thioether substituent on the solid state and solution properties of N3S-ligated copper(ii) complexes

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Publication details

The article was received on 30 Apr 2003, accepted on 13 Jun 2003 and first published on 30 Jun 2003


Article type: Paper
DOI: 10.1039/B304846B
Citation: Dalton Trans., 2003,0, 3111-3116
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    Evaluation of the influence of a thioether substituent on the solid state and solution properties of N3S-ligated copper(II) complexes

    K. J. Tubbs, A. L. Fuller, B. Bennett, A. M. Arif, M. M. Makowska-Grzyska and L. M. Berreau, Dalton Trans., 2003, 0, 3111
    DOI: 10.1039/B304846B

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