Effects of electron-deficient β-diketiminate and formazan supporting ligands on copper(I)-mediated dioxygen activation

Sungjun Hong, Lyndal M.R. Hiii, Aalo K. Gupta, Benjamin D. Naab, Joe B. Gllroy, Robin G. Hicks, Christopher J. Cramer, William B. Tolman

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Abstract

Copper(I) complexes of a diketiminate featuring CF 3 groups on the backbone and dimethylphenyl substituents (4) and a nitroformazan (5) were synthesized and shown by spectroscopy, X-ray crystallography, cyclic voltammetry, and theory to contain copper(l) sites electron-deficient relative to those supported by previously studied diketiminate complexes comprising alkyl or aryl backbone substituents. Despite their electron-poor nature, oxygenation of LCu(CH3CN) (L = 4 or 5) at room temperature yielded bis(hydroxo)dicopper(II) compounds and at -80 0C yielded bis(w-oxo)dicopper complexes that were identified on the basis of UV-vis and resonance Raman spectroscopy, spectrophotometric titration results (2:1 Cu/02 ratio), electron paramagnetic resonance spectroscopy (silent), and density functional theory calculations. The bis(w-oxo)dicopper complex supported by 5 exhibited unusual spectroscopic properties and decayed via a novel intermediate proposed to be a metallaverdazyl radical complex, findings that highlight the potential for the formazan ligand to exhibit "noninnocent" behavior.

Original languageEnglish (US)
Pages (from-to)4514-4523
Number of pages10
JournalInorganic chemistry
Volume48
Issue number10
DOIs
StatePublished - May 18 2009

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    Hong, S., Hiii, L. M. R., Gupta, A. K., Naab, B. D., Gllroy, J. B., Hicks, R. G., Cramer, C. J., & Tolman, W. B. (2009). Effects of electron-deficient β-diketiminate and formazan supporting ligands on copper(I)-mediated dioxygen activation. Inorganic chemistry, 48(10), 4514-4523. https://doi.org/10.1021/ic9002466