Issue 16, 2022

Conformationally dynamic copper coordination complexes

Abstract

The interplay between oxidation state and coordination geometry dictates both kinetic and thermodynamic properties underlying electron transfer events in copper coordination complexes. An ability to stabilize both CuI and CuII oxidation states in a single conformationally dynamic chelating ligand allows access to controlled redox reactivity. We report an analysis of the conformational dynamics of CuI complexes bearing dipicolylaniline (dpaR) ligands, with ortho-aniline substituents R = H and R = OMe. Variable temperature NMR spectroscopy and electrochemical experiments suggest that in solution at room temperature, an equilibrium exists between two conformers. Two metal-centered redox events are observed which, bolstered by structural information from single crystal X-ray diffraction and solution information from EPR and NMR spectroscopies, are ascribed to the CuII/I couple in planar and tetrahedral conformations. Activation and equilibrium parameters for these structural interconversions are presented and provide entry to leveraging redox-triggered conformational dynamics at Cu.

Graphical abstract: Conformationally dynamic copper coordination complexes

Supplementary files

Article information

Article type
Paper
Submitted
01 2 2022
Accepted
19 3 2022
First published
21 3 2022

Dalton Trans., 2022,51, 6212-6219

Conformationally dynamic copper coordination complexes

B. J. Charette, P. J. Griffin, C. M. Zimmerman and L. Olshansky, Dalton Trans., 2022, 51, 6212 DOI: 10.1039/D2DT00312K

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