%0 Journal Article %1 Noll_2022 %A Noll, Niklas %A Krause, Ana-Maria %A Beuerle, Florian %A Würthner, Frank %D 2022 %I Springer Science and Business Media LLC %J Nature Catalysis %K myown %N 10 %P 867--877 %R 10.1038/s41929-022-00843-x %T Enzyme-like water preorganization in a synthetic molecular cleft for homogeneous water oxidation catalysis %U https://doi.org/10.1038%2Fs41929-022-00843-x %V 5 %X Inspired by the proficiency of natural enzymes, mimicking of nanoenvironments for precise substrate preorganization is a promising strategy in catalyst design. However, artificial examples of enzyme-like activation of H2O 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 H2O molecules in front of the metal centre 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 seventh H2O ligand directly coordinated to a RuIII centre. Another H2O substrate is preorganized via a well-defined hydrogen-bonding network for the crucial O–O bond formation by nucleophilic attack.

@article{Noll_2022, abstract = {Inspired by the proficiency of natural enzymes, mimicking of nanoenvironments for precise substrate preorganization is a promising strategy in catalyst design. However, artificial examples of enzyme-like activation of H2O 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 H2O molecules in front of the metal centre 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 seventh H2O ligand directly coordinated to a RuIII centre. Another H2O substrate is preorganized via a well-defined hydrogen-bonding network for the crucial O–O bond formation by nucleophilic attack.}, added-at = {2022-11-24T12:31:02.000+0100}, author = {Noll, Niklas and Krause, Ana-Maria and Beuerle, Florian and Würthner, Frank}, biburl = {https://www.bibsonomy.org/bibtex/226794b70454d1106fb0cb93c43600f79/wuerthner_group}, doi = {10.1038/s41929-022-00843-x}, interhash = {644706254561f84fc96819d9dec93ead}, intrahash = {26794b70454d1106fb0cb93c43600f79}, journal = {Nature Catalysis}, keywords = {myown}, month = oct, number = 10, pages = {867--877}, publisher = {Springer Science and Business Media {LLC}}, timestamp = {2022-11-24T12:31:02.000+0100}, title = {Enzyme-like water preorganization in a synthetic molecular cleft for homogeneous water oxidation catalysis}, url = {https://doi.org/10.1038%2Fs41929-022-00843-x}, volume = 5, year = 2022 }