- AutorIn
- Mohammad A. Abdulmalic
- Azar Aliabadi
- Andreas Petr
- Yulia Krupskaya
- Vladislav Kataev
- Bernd Büchner
- Torsten Hahn
- Jens Kortus
- Tobias Rüffer
- Titel
- 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
- Zitierfähige Url:
- https://nbn-resolving.org/urn:nbn:de:bsz:14-qucosa-138948
- Quellenangabe
- Dalton transactions 2012;41:14657–14670, ISSN: 1477-9226
- Erstveröffentlichung
- 2012
- Abstract (DE)
- Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
- Abstract (EN)
- 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.
- Andere Ausgabe
- DOI: 10.1039/c2dt31802d
- Volltext des Artikels, der zuerst in der Zeitschrift "Dalton transactions" des Royal Society of Chemistry-Verlages erschienen ist.
Link: http://dx.doi.org/10.1039/c2dt31802d - Freie Schlagwörter (DE)
- Elektronenspinresonanz, Kupferhaltige Komplexe, Kristallstruktur, Liganden, Nickelkomplexe
- Freie Schlagwörter (EN)
- electron paramagnetic resonance, copper(II) complexes, crystal-structure, (NiCuNiII)-Cu-II-Ni-II complexes, nickel(II) complexes, atomic parameters, basis-sets, ligands, exchange
- Klassifikation (DDC)
- 540
- Klassifikation (RVK)
- VA 1120
- Verlag
- Royal Society of Chemistry, Cambridge
- Förder- / Projektangaben
- URN Qucosa
- urn:nbn:de:bsz:14-qucosa-138948
- Veröffentlichungsdatum Qucosa
- 08.04.2014
- Dokumenttyp
- Artikel
- Sprache des Dokumentes
- Englisch
- Lizenz / Rechtehinweis