Enzyme-like water preorganization in a synthetic molecular cleft for homogeneous water oxidation catalysis
Please always quote using this URN: urn:nbn:de:bvb:20-opus-302897
- 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. TheInspired 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.…
Author: | Niklas Noll, Ana-Maria Krause, Florian Beuerle, Frank WürthnerORCiDGND |
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URN: | urn:nbn:de:bvb:20-opus-302897 |
Document Type: | Journal article |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Organische Chemie |
Language: | English |
Parent Title (German): | Nature Catalysis |
Year of Completion: | 2022 |
Edition: | accepted version |
Source: | Nature Catalysis (2022) 5: 867–877. https://doi.org/10.1038/s41929-022-00843-x |
DOI: | https://doi.org/10.1038/s41929-022-00843-x |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 547 Organische Chemie |
Tag: | catalysis; catalyst synthesis; catalytic mechanisms; enzyme; homogeneous catalysis; molecular; photocatalysis; supramolecular chemistry; water oxidation |
Release Date: | 2023/02/15 |
Embargo Date: | 2023/04/03 |
EU-Project number / Contract (GA) number: | 787937 |
OpenAIRE: | OpenAIRE |
Note: | This version of the article has been accepted for publication, after peer review and is subject to Springer Nature’s AM terms of use (https://www.springernature.com/gp/open-research/policies/accepted-manuscript-terms), but is not the Version of Record and does not reflect post-acceptance improvements, or any corrections. The Version of Record is available online at: https://doi.org/10.1038/s41929-022-00843-x |
Licence (German): | Deutsches Urheberrecht |