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Article Dans Une Revue Chemistry - A European Journal Année : 2013

Stable anilinyl radicals coordinated to nickel: X-ray crystal structure and characterization

Résumé

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 (E1/2=-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 0.02Å 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 Cortho-Cmeta 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.

Dates et versions

hal-00917666 , version 1 (12-12-2013)

Identifiants

Citer

A. Kochem, G. Gellon, N. Leconte, B. Baptiste, C. Philouze, et al.. Stable anilinyl radicals coordinated to nickel: X-ray crystal structure and characterization. Chemistry - A European Journal, 2013, 19, pp.16707-16721. ⟨10.1002/chem.201303228⟩. ⟨hal-00917666⟩
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