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Issue 48, 2012
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An interplay between the spin density distribution and magnetic superexchange interactions: a case study of mononuclear [nBu4N]2[Cu(opooMe)] and novel asymmetric trinuclear [Cu3(opooMe)(pmdta)2](NO3)2·3MeCN

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Abstract

Treatment of the diethyl ester of o-phenylenebis(oxamic acid) (opbaH2Et2, 1) with 5/6 equivalent of MeNH2 in abs. EtOH results in the exclusive formation of the ethyl ester of o-phenylene(N′-methyl oxamide)(oxamic acid) (opooH3EtMe, 2) in ca. 50% yield. Treatment of 2 with four equivalents of [Me4N]OH followed by the addition of Cu(ClO4)2·6H2O gave [Me4N]2[Cu(opooMe)]·H2O (3A) in ca. 80% yield. As 3A appears to be a hygroscopic solid, the related [nBu4N]+ salts [nBu4N]2[M(opooMe)]·H2O (M = Cu (3B), Ni (4)) have been synthesized. By addition of two equivalents of [Cu(pmdta)(NO3)2] to a MeCN solution of 3B the novel asymmetric trinuclear complex [Cu3(opooMe)(pmdta)2](NO3)2 (5) could be obtained in ca. 90% yield. Compounds 2, 3A, 3B, 4 and 5 have been characterized by elemental analysis and NMR/IR spectroscopy. Furthermore, the solid state structures of 3A in the form of [Me4N]2[Cu(opooMe)]·MeOH (3A′), 3B in the form of [nBu4N]2[Cu(opooMe)] (3B′), 4 in the form of [nBu4N]2[Ni(opooMe)]·1.25H2O (4′) and 5 in the form of [Cu3(opooMe)(pmdta)2] (NO3)2·3MeCN (5′), respectively, have been determined by single-crystal X-ray diffraction studies. By controlled cocrystallization, diamagnetically diluted 3B (1%) in the host lattice of 4 (99%) in the form of single crystals have been made available, allowing single crystal EPR studies to extract all components of the g-factor and the tensors of onsite CuA and transferred NA hyperfine interaction. Out of these studies the spin density distribution of the [Cu(opooMe)]2− complex fragment could be determined. The magnetic properties of 5 were studied by susceptibility measurements versus temperature. An intramolecular J parameter of −65 cm−1 has been obtained, unexpectedly, as 5 should possess two different J values due to its two different spacers between the adjacent CuII ions, namely an oxamate (C2NO3) and an oxamidate (C2N2O2) fragment. This unexpected result is explained by a summarizing discussion of the experimentally obtained EPR results (spin density distribution) of 3B, the geometries of the terminal [Cu(pmdta)]2+ fragments of 5 determined by X-ray crystallographic studies and accompanying quantum chemical calculations of the spin density distribution of the mononuclear [Cu(opooMe)]2− and of the magnetic exchange interactions of trinuclear [Cu3(opooMe)(pmdta)2]2+ complex fragments.

Graphical abstract: An interplay between the spin density distribution and magnetic superexchange interactions: a case study of mononuclear [nBu4N]2[Cu(opooMe)] and novel asymmetric trinuclear [Cu3(opooMe)(pmdta)2](NO3)2·3MeCN

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Supplementary files

Article information


Submitted
07 Aug 2012
Accepted
26 Sep 2012
First published
03 Oct 2012

Dalton Trans., 2012,41, 14657-14670
Article type
Paper

An interplay between the spin density distribution and magnetic superexchange interactions: a case study of mononuclear [nBu4N]2[Cu(opooMe)] and novel asymmetric trinuclear [Cu3(opooMe)(pmdta)2](NO3)2·3MeCN

M. A. Abdulmalic, A. Aliabadi, A. Petr, Y. Krupskaya, V. Kataev, B. Büchner, T. Hahn, J. Kortus and T. Rüffer, Dalton Trans., 2012, 41, 14657
DOI: 10.1039/C2DT31802D

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