A Gas‐Phase CanMn4−nO4+ Cluster Model for the Oxygen‐Evolving Complex of Photosystem II
Abstract
One of the fundamental processes in nature, the oxidation of water, is catalyzed by a small CaMn3O4⋅MnO cluster located in photosystem II (PS II). Now, the first successful preparation of a series of isolated ligand‐free tetrameric CanMn4−nO4+ (n=0–4) cluster ions is reported, which are employed as structural models for the catalytically active site of PS II. Gas‐phase reactivity experiments with D2O and H218O in an ion trap reveal the facile deprotonation of multiple water molecules via hydroxylation of the cluster oxo bridges for all investigated clusters. However, only the mono‐calcium cluster CaMn3O4+ is observed to oxidize water via elimination of hydrogen peroxide. First‐principles density functional theory (DFT) calculations elucidate mechanistic details of the deprotonation and oxidation reactions mediated by CaMn3O4+ as well as the role of calcium.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- May 14, 2019
- Source ID
- 10.1002/anie.201903738
Entities
People
- Irene Fleischer
- Robert N Barnett
- Sandra M Lang
- Silvia Mauthe
- Thorsten M. Bernhardt
- Uzi Landman
Organizations
- Air Force Office of Scientific Research
- Georgia Tech
- German Research Foundation
- Ulm University