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

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 (E (1/2)=−0.45 V and +0.82 V (vs. Fc/Fc(+))). A linear C(NHC)‐Cu‐C(NHC) arrangement and hemilability of the two pyridine donors allows the ligand to adapt to the different stereoelectronic and coordination requirements of Cu(I) versus Cu(II)/Cu(III). Analytical methods such as NMR, UV/Vis, IR, electron paramagnetic resonance, and Cu Kβ 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 Cu(I), Cu(II), and Cu(III) species. Facile 2‐electron interconversion combined with the exposure of two basic pyridine N sites in the reduced Cu(I) form suggest that [LCu](+/2+/3+) may operate in catalysis via coupled 2 e(−)/2 H(+) transfer.