Filtern
Volltext vorhanden
- ja (1)
Gehört zur Bibliographie
- ja (1)
Erscheinungsjahr
- 2022 (1)
Dokumenttyp
- Artikel / Aufsatz in einer Zeitschrift (1) (entfernen)
Sprache
- Englisch (1) (entfernen)
Schlagworte
- enzyme (1) (entfernen)
Institut
- Institut für Organische Chemie (1) (entfernen)
EU-Projektnummer / Contract (GA) number
- 787937 (1)
Inspired by the proficiency of natural enzymes, mimicking of nanoenvironments for precise substrate preorganisation is a promising strategy in catalyst design. However, artificial examples of enzyme-like activation of H\(_2\)O molecules for the challenging oxidative water splitting reaction are hardly explored. Here, we introduce a mononuclear Ru(bda) complex (M1, bda: 2,2’-bipyridine-6,6’-dicarboxylate) equipped with a bipyridine-functionalized ligand to preorganize H\(_2\)O molecules in front of the metal center as in enzymatic clefts. The confined pocket of M1 accelerates chemically driven water oxidation at pH 1 by facilitating a water nucleophilic attack pathway with a remarkable turnover frequency of 140 s\(^{−1}\) that is comparable to the oxygen-evolving complex of photosystem II. Single crystal X-ray analysis of M1 under catalytic conditions allowed the observation of a 7th H\(_2\)O ligand directly coordinated to a RuIII center. Via a well-defined hydrogen-bonding network, another H\(_2\)O substrate is preorganized for the crucial O–O bond formation via nucleophilic attack.