NDLI: Radical Localization in a Series of Symmetric $Ni^{II}$ Complexes with Oxidized Salen Ligands

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Radical Localization in a Series of Symmetric $Ni^{II}$ Complexes with Oxidized Salen Ligands

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Chiang, Linus Shimazaki, Yuichi Ogura, Takashi Kochem, Amélie Sakaguchi, Miyuki Dunn, Tim J. Thomas, Fabrice Storr, Tim Vezin, Hervé Orio, Maylis Jarjayes, Olivier
Description	Author Affiliation: Chiang L ( Department of Chemistry, Simon Fraser University, British Columbia, Canada.)
Abstract	Square-planar nickel(II) complexes of salen ligands, N,N′-bis(3-tert-butyl-(5R)-salicylidene)-1,2-cyclohexanediamine), in which R=tert-butyl (1), OMe (2), and $NMe_{2}$ (3), were prepared and the electronic structure of the one-electron-oxidized species $[1–3]^{+.}$ was investigated in solution. Cyclic voltammograms of [1–3] showed two quasi-reversible redox waves that were assigned to the oxidation of the phenolate moieties to phenoxyl radicals. From the difference between the first and second redox potentials, the trend of electronic delocalization $1^{+.}>2^{+.}>3^{+.}$ was obtained. The cations $[1–3]^{+.}$ exhibited isotropic g tensors of 2.045, 2.023, and 2.005, respectively, reflecting a lower metal character of the singly occupied molecular orbital (SOMO) for systems that involve strongly electron-donating substituents. Pulsed-EPR spectroscopy showed a single population of equivalent imino nitrogen atoms for $1^{+.},$ whereas two distinct populations were observed for $2^{+.}.$ The resonance Raman spectra of $2^{+.}$ and $3^{+.}$ displayed the $ν_{8a}$ band of the phenoxyl radicals at $1612 cm^{−1},$ as well as the $ν_{8a}$ bands of the phenolates. In contrast, the Raman spectrum of $1^{+.}$ exhibited the $ν_{8a}$ band at $1602 cm^{−1},$ without any evidence of the phenolate peak. Previous work showed an intense near-infrared (NIR) electronic transition for $1^{+.}$ $(Δν_{1/2}=660 cm^{−1},$ $ε=21 700 M^{−1} cm^{−1}),$ indicating that the electron hole is fully delocalized over the ligand. The broader and moderately intense NIR transition of $2^{+.}$ $(Δν_{1/2}=1250 cm^{−1},$ $ε=12 800 M^{−1} cm^{−1})$ suggests a certain degree of ligand-radical localization, whereas the very broad NIR transition of $3^{+.}$ $(Δν_{1/2}=8630 cm^{−1},$ $ε=2550 M^{−1} cm^{−1})$ indicates significant localization of the ligand radical on a single ring. Therefore, $1^{+.}$ is a Class III mixed-valence complex, $2^{+.}$ is Class II/III borderline complex, and $3^{+.}$ is a Class II complex according to the Robin–Day classification method. By employing the Coulomb-attenuated method (CAM-B3LYP) we were able to predict the electron-hole localization and NIR transitions in the series, and show that the energy match between the redox-active ligand and the metal d orbitals is crucial for delocalization of the radical SOMO.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	44
Volume Number	18
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2012-10-29
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Coordination Complexes Chemistry Ethylenediamines Nickel Electron Spin Resonance Spectroscopy Ions Ligands Oxidation-Reduction Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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