Synthesis, crystallographic and spectroscopic characterization, and theoretical elucidation of an elusive aminyl radical containing a Cu-II-aminyl-iminosemiquinone complex

An elusive aminyl radical and an iminosemiquinone radical-coordinated square pyramidal Cu(ii) complex (1) have been isolated by the reaction between the noninnocent ligand H4LPy(AP) and Cu(ClO4)(2)center dot 6H(2)O in the presence of Et3N and air as the sole oxidant. The geometry and electronic stru...

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Bibliographic Details
Published inChemical communications (Cambridge, England) Vol. 57; no. 11; pp. 1352 - 1355
Main Authors Sarkar, Prasenjit, Sarmah, Amrit, Mukherjee, Chandan
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 07.02.2021
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
OXIDATION
ALCOHOLS
ELECTRON
TRANSITION-METAL-COMPLEXES
LIGANDS
REACTIVITY
NITROGEN
COORDINATION
GENERATION
H AMINATION
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Summary:An elusive aminyl radical and an iminosemiquinone radical-coordinated square pyramidal Cu(ii) complex (1) have been isolated by the reaction between the noninnocent ligand H4LPy(AP) and Cu(ClO4)(2)center dot 6H(2)O in the presence of Et3N and air as the sole oxidant. The geometry and electronic structure of the complex were concluded by X-ray crystallography, magnetic and EPR measurements, and density functional theory (DFT) calculations. This work reports the first crystallographic example of the two different types of radicals co-existing in a stable complex.
ISSN:1359-7345
1364-548X
DOI:10.1039/d0cc07378d