Journal
INORGANICA CHIMICA ACTA
Volume 406, Issue -, Pages 153-159Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2013.07.022
Keywords
Nickel; O-ligands; Structure elucidation; Electronic structure; EPR spectroscopy; Magnetic properties
Categories
Funding
- RFBR [13-03-01000]
- Russian President Grant supporting scientific schools [NSh-1113.2012.3]
- Program of Presidium of RAS [8]
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A number of square-planar bis-o-semiquinonato nickel complexes were obtained by the reaction of tetracarbonylnickel(0) with the derivatives of 3,6-di-tert-butyl-benzoquinone-1,2. Structural investigation of two complexes having annulated rings (N, N'-piperazino- and O,O'-1,2-ethanediolato-) in 4,5-back positions of quinonato ring detected square-planar molecular geometry. All complexes were studied by H-1 NMR, NIR-IR spectroscopy, magnetic susceptibility. Each compound has intensive absorption band in NIR-region which is attributed to b(1u) -> b*(3g) (in D-2h point symmetry) ligand based transition. Magnetic measurements indicate only one complex (with O,O'-1,2-ethanediolato - substituent) having magnetic moment corresponding to two noninteracting unpaired electrons (2.45 mu(B)). Magnetic moments of the other complexes are essentially lower and correspond to so-called singlet diradical character of complexes. So, in general, the order of frontier orbitals does not depend on the electronic properties of substituents in o-semiquinonato ligands with one mentioned exception. (C) 2013 Elsevier B.V. All rights reserved.
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