An Adaptable N‐Heterocyclic Carbene Macrocycle Hosting Copper in Three Oxidation States
In: Angewandte Chemie (International Ed. in English), Jg. 59 (2020), Heft 14, S. 5696-5705
Online
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Zugriff:
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 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 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 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.
A neutral hybrid macrocycle L with two trans‐positioned N‐heterocyclic carbene (NHC) and two pyridine donors can adapt to the different geometric and electronic preferences of CuI, CuII, and CuIII. This allows isolation of a series of complexes hosting Cu in all three oxidation states, and their reversible interconversion at moderate potentials and with minor structural rearrangement.
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An Adaptable N‐Heterocyclic Carbene Macrocycle Hosting Copper in Three Oxidation States
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Autor/in / Beteiligte Person: | Meyer, Franc ; Demeshko, Serhiy ; Resch, Stefan G. ; Kühn, Fritz E. ; Liu, Yang ; Klawitter, Iris ; Dechert, Sebastian ; Cutsail, George E. ; DeBeer, Serena |
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Zeitschrift: | Angewandte Chemie (International Ed. in English), Jg. 59 (2020), Heft 14, S. 5696-5705 |
Veröffentlichung: | John Wiley and Sons Inc., 2020 |
Medientyp: | unknown |
ISSN: | 1521-3773 (print) ; 1433-7851 (print) |
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