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

Journal Article · · Angewandte Chemie
ORCiD logo [1]; ORCiD logo [1];  [1];  [2];  [1];  [1];  [3];  [2]; ORCiD logo [1]
  1. Institute of Inorganic Chemistry University of Göttingen Tammannstrasse 4 37077 Göttingen Germany
  2. Department of Inorganic Spectroscopy Max Planck Institute for Chemical Energy Conversion Stiftstrasse 34–36 45470 Mülheim an der Ruhr Germany
  3. Department of Chemistry &, Catalysis Research Center Technische Universität München Lichtenbergstrasse 4 85748 Garching bei München Germany
+ Show Author Affiliations

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 ( 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.

Sponsoring Organization:
USDOE
OSTI ID:
1594199
Alternate ID(s):
OSTI ID: 1594201
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 132 Journal Issue: 14; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

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