Synthesis, structures, and magnetic properties of binuclear carboxylate complexes with NiII and NiIII atoms |
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| Authors: | I. L. Eremenko M. A. Golubnichaya S. E. Nefedov A. A. Sidorov I. F. Golovaneva V. I. Burkov O. G. Ellert V. M. Novotortsev L. T. Ermenko A. Sousa M. R. Bermejo |
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| Affiliation: | (1) N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky prosp., 117907 Moscow, Russian Federation;(2) Moscow Physicotechnical Institute, 9 Institutskii per., 141700 Dolgoprudnyi, Moscow Region, Russian Federation;(3) Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences, 142432 Chrnogolovka, Moscow Region, Russian Federation;(4) Department of Inorganic Chemistry, University of Santiago de Compostela, 15706 Santiago de Compostela, Spain |
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| Abstract: | ![]()
The reaction of NiCl2·6H2O with Me3CCOOH and KOH taken in a molar ratio of 1:2:2 in water afforded the nonanuclear antiferromagnetic complex Py2Ni2(Me3CCOOH)2(OOCCMe3)2(μ-OOCCMe3)2(μ-OH2), which apparently contains NiII and NiIII atoms. The complex was isolated by extraction with CH2Cl2, benzene, or hexane. The reactions of this complex with pyridine bases (pyridine (Py), 3,4-lutidine (Lut), and nicorandil (Nic)) gave the adducts L4Ni2(OOCCMe3)2(μ-OOCCMe3)2(μ-OH) (L=Py, Lut, or Nic, respectively). According to magnetic measurements, intramolecular ferromagnetic exchange interactions in these adducts are complemented by intermolecular antiferromagnetic interactions. Pyrolysis of the pyridine adduct in air or under an inert atmosphere in xylene yielded the antiferromagnetic complex Py2Ni2(Me3CCOOH)2(OOCCMe3)2(μ-OOCCMe3)2(μ-OH2), which contains NiII atoms. The structures of all the complexes synthesized were established by X-ray diffraction analysis. The electronic absorption spectra of these compounds are considered. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 725–738, April, 1998. |
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| Keywords: | nickel clusters mixed-valence complexes carboxylate ligands X-ray diffraction analysis magnetic properties UV and IR spectra |
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