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Synthesis, characterization and magnetic properties of new homotrinuclear copper(II) complexes
Authors:Tobias Rüffer  Björn Bräuer  Ian Hewitt
Institution:a Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie, Strasse der Nationen 62, D-09107 Chemnitz, Germany
b Universität Karlsruhe, Institut für Anorganische Chemie, Engestrasse 15, D-76131 Karlsruhe, Germany
c Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Physik, Reichenhainer Strasse. 70, D-09107 Chemnitz, Germany
Abstract:Two new mononuclear bis(oxamato) complexes with the formula nBu4N]2M(nabo)] M = Ni (4), Cu (5), with nabo = 2,3-naphthalene-bis(oxamato) have been synthesized as precursors for trinuclear oxamato-bridged transition metal complexes. Starting from 5 the homo-trinuclear complex Cu3(nabo)(pmdta)2(BF4)](BF4) · MeCN · Et2O (7), with pmdta = N,N,N′,N″,N″-pentamethyldiethylenetriamine, has been prepared. The central N,N′-2,3-naphthalene bridge of 7 is so far the most extended π-conjugated bridge of trinuclear bis(oxamato) type transition metal complexes. The goal of this work was to verify the N,N′-2,3-naphthalene bridge of 7 on its magnetic properties in comparison to the N,N′-o-phenylene bridge of the related homo-trinuclear complex Cu3(opba)(pmdta)2(NO3)](NO3) · 2MeCN (6) (opba = o-phenylene-bis(oxamato)). The crystal structures of 4-7 were solved. The magnetic properties of 6 and 7 were studied by susceptibility measurements versus temperature. For the intramolecular J parameter, values of −89 cm−1 (6) and −113 cm−1 (7) were obtained. The different J values are discussed based on the crystal structures of 6 and 7.
Keywords:Flexidentate ligands  Oxamato ligands  Magnetochemistry  Copper  Nickel  X-ray diffraction
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