Fully Delocalized Mixed-Valent Cu1.5 Cu1.5 Complex: Strong Cu-Cu interaction and Fast Electron Self-Exchange Rate Despite Large Structural Changes.

A flexible macrocyclic ligand with two tridentate {CNC} compartments can host two Cu ions in reversibly interconvertible states, CuI CuI (1) and mixed-valent Cu1.5 Cu1.5 (2). They were characterized by XRD and multiple spectroscopic methods, including EPR, UV/Vis absorption and MCD, in combination with TD-DFT and CASSCF calculations. 2 features a short Cu⋅⋅⋅Cu distance (≈2.5 Å; compared to ≈4.0 Šin 1) and a very high delocalization energy of 13 000 cm-1 , comparable to the mixed-valent state of the biological CuA site. Electron self-exchange between 1 and 2 is rapid despite large structural reorganization, and is proposed to proceed via a sequential mechanism involving an active conformer of 1, viz. 1'; the latter has been characterized by XRD. Such electron transfer (ET) process is reminiscent of the conformationally gated ET proposed for biological systems. This redox couple is a unique pair of flexible dicopper complexes, achieving fast electron self-exchange closely related to the function of the CuA site.

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 (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 Kß 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.