Conformationally dynamic copper coordination complexes

Bronte J. Charette, Paul J. Griffin, Claire M. Zimmerman, Lisa Olshansky

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish (US)
JournalDalton Transactions
DOIs
StateAccepted/In press - 2022

ASJC Scopus subject areas

  • Inorganic Chemistry

Fingerprint

Dive into the research topics of 'Conformationally dynamic copper coordination complexes'. Together they form a unique fingerprint.

Cite this