| Autor: |
Liu Y; Institute of Inorganic Chemistry, University of Göttingen, Tammannstraße 4, 37077 Göttingen, Germany., Chatterjee S; Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr, Germany., Cutsail GE 3rd; Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr, Germany.; Institute of Inorganic Chemistry, University of Duisburg-Essen, Universitätsstraße 7, 45117 Essen, Germany., Peredkov S; Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr, Germany., Gupta SK; Institute of Inorganic Chemistry, University of Göttingen, Tammannstraße 4, 37077 Göttingen, Germany., Dechert S; Institute of Inorganic Chemistry, University of Göttingen, Tammannstraße 4, 37077 Göttingen, Germany., DeBeer S; Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr, Germany., Meyer F; Institute of Inorganic Chemistry, University of Göttingen, Tammannstraße 4, 37077 Göttingen, Germany.; International Center for Advanced Studies of Energy Conversion (ICASEC), University of Göttingen, Tammannstraße 6, 37077 Göttingen, Germany. |
| Abstrakt: |
The active site of nitrous oxide reductase (N 2 OR), a key enzyme in denitrification, features a unique μ 4 -sulfido-bridged tetranuclear Cu cluster (the so-called Cu Z or Cu Z * site). Details of the catalytic mechanism have remained under debate and, to date, synthetic model complexes of the Cu Z */Cu Z sites are extremely rare due to the difficulty in building the unique {Cu 4 (μ 4 -S)} core structure. Herein, we report the synthesis and characterization of [Cu 4 (μ 4 -S)] n+ ( n = 2, 2 ; n = 3, 3 ) clusters, supported by a macrocyclic {py 2 NHC 4 } ligand (py = pyridine, NHC = N -heterocyclic carbene), in both their 0-hole ( 2 ) and 1-hole ( 3 ) states, thus mimicking the two active states of the Cu Z * site during enzymatic N 2 O reduction. Structural and electronic properties of these {Cu 4 (μ 4 -S)} clusters are elucidated by employing multiple methods, including X-ray diffraction (XRD), nuclear magnetic resonance (NMR), UV/vis, electron paramagnetic resonance (EPR), Cu/S K-edge X-ray emission spectroscopy (XES), and Cu K-edge X-ray absorption spectroscopy (XAS) in combination with time-dependent density functional theory (TD-DFT) calculations. A significant geometry change of the {Cu 4 (μ 4 -S)} core occurs upon oxidation from 2 (τ 4 (S) = 0.46, seesaw) to 3 (τ 4 (S) = 0.03, square planar), which has not been observed so far for the biological Cu Z (*) site and is unprecedented for known model complexes. The single electron of the 1-hole species 3 is predominantly delocalized over two opposite Cu ions via the central S atom, mediated by a π/π superexchange pathway. Cu K-edge XAS and Cu/S K-edge XES corroborate a mixed Cu/S-based oxidation event in which the lowest unoccupied molecular orbital (LUMO) has a significant S-character. Furthermore, preliminary reactivity studies evidence a nucleophilic character of the central μ 4 -S in the fully reduced 0-hole state. |
