An Adaptable N-Heterocyclic Carbene Macrocycle Hosting Copper in Three Oxidation States.

ABSTRACT: A neutral hybrid macrocycle with two trans-positioned N-heterocyclic carbenes (NHCs) and two pyridine donors hosts copper in three oxidation states (+I-+III) in a series of structurally characterized complexes (1-3). Redox interconversion of [LCu]+/2+/3+ is electrochemically (quasi)reversible and occurs at moderate potentials (E1/2 =-0.45?V and +0.82?V (vs. Fc/Fc+ )). A linear CNHC -Cu-CNHC arrangement and hemilability of the two pyridine donors allows the ligand to adapt to the different stereoelectronic and coordination requirements of CuI versus CuII /CuIII . Analytical methods such as NMR, UV/Vis, IR, electron paramagnetic resonance, and Cu K? high-energy-resolution fluorescence detection X-ray absorption spectroscopies, as well as DFT calculations, give insight into the geometric and electronic structures of the complexes. The XAS signatures of 1-3 are textbook examples for CuI , CuII , and CuIII species. Facile 2-electron interconversion combined with the exposure of two basic pyridine N sites in the reduced CuI form suggest that [LCu]+/2+/3+ may operate in catalysis via coupled 2?e- /2?H+ transfer.

SUBMITTER: Liu Y 

PROVIDER: S-EPMC7154638 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature