Synthesis, crystallographic and spectroscopic characterization, and theoretical elucidation of an elusive aminyl radical containing a CuII–aminyl-iminosemiquinone complex (Dedicated to Professor Wolfgang Kaim on the occasion of his 70th birthday.)

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)2·6H2O in the presence of Et3N and air as the sole oxidant. The geometry and electronic structure of the c...

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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 Society of Chemistry 07.02.2021
Subjects
Chemical synthesis
Coordination compounds
Crystallography
Density functional theory
Electronic structure
Ligands
Mathematical analysis
Molecular structure
Oxidizing agents
Structural analysis
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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)2·6H2O 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.
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ISSN:1359-7345
1364-548X
DOI:10.1039/d0cc07378d