期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 19, 期 49, 页码 16707-16721出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201303228
关键词
aminyl; aniline; ligands; nickel; radicals; X-ray diffraction
资金
- DCM
- Labex Arcane (Universite Joseph Fourier, Grenoble)
Two anilinosalen and a mixed phenol-anilinosalen ligands involving sterically hindered anilines moieties were synthesized. Their nickel(II) complexes 1, 2, and 3 were prepared and characterized. They could be readily one-electron oxidized (E-1/2=-0.30, -0.26 and 0.10V vs. Fc(+)/Fc, respectively) into anilinyl radicals species [1](+), [2](+), and [3](+), respectively. The radical complexes are extremely stable and were isolated as single crystals. X-ray crystallographic structures reveal that the changes in bond length resulting from oxidation do not exceed 0.02 angstrom within the ligand framework in the symmetrical [1](+) and [2](+). No quinoid bond pattern was present. In contrast, larger structural rearrangements were evidenced for the unsymmetrical [3](+), with shortening of one CorthoCmeta bond. Radical species [1](+) and [2](+) exhibit a strong absorption band at around 6000cm(-1) (class III mixed valence compounds). This band is significantly less intense than [3](+), consistent with a rather localized anilinyl radical character, and thus a classification of this species as class II mixed-valence compound. Magnetic and electronic properties, as well as structural parameters, have been computed by DFT methods.
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