Dispersion forces drive water oxidation in molecular ruthenium catalysts

Johansson, Mikael P.; Niederegger, Lukas; Rauhalahti, Markus; Hess, Corinna R.; Kaila, Ville R. I.

doi:10.1039/d0ra09004b

Cited by 5 publications

(5 citation statements)

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Although the present O 2 end -on configuration differs from the typical side -on coordination in Ni-O 2 complexes of other dioxygenases, the proposed O 2 – splitting process resembles a Criegee rearrangement in non-heme iron intradiol dioxygenases, as well as an alkylperoxo-intermediate observed in extradiol-ring cleaving dioxygenases . Moreover, similar peroxo-intermediates have been proposed for O–O bond splitting in oxidoreductases like cytochrome c oxidase or apocarotenoid oxygenase (see Figure S10 for comparison to AsqJ), as well as in enzymatic and molecular H 2 O-splitting catalysts, such as photosystem II , and Ru-catalysts, respectively.…”

Section: Discussionsupporting

confidence: 58%

Peroxy Intermediate Drives Carbon Bond Activation in the Dioxygenase AsqJ

et al. 2022

Self Cite

View full text Add to dashboard Cite

Dioxygenases catalyze stereoselective oxygen atom transfer in metabolic pathways of biological, industrial, and pharmaceutical importance, but their precise chemical principles remain controversial. The α-ketoglutarate (αKG)-dependent dioxygenase AsqJ synthesizes biomedically active quinolone alkaloids via desaturation and subsequent epoxidation of a carbon−carbon bond in the cyclopeptin substrate. Here, we combine high-resolution X-ray crystallography with enzyme engineering, quantum-classical (QM/MM) simulations, and biochemical assays to describe a peroxidic intermediate that bridges the substrate and active site metal ion in AsqJ. Homolytic cleavage of this moiety during substrate epoxidation generates an activated high-valent ferryl (Fe IV = O) species that mediates the next catalytic cycle, possibly without the consumption of the metabolically valuable αKG cosubstrate. Our combined findings provide an important understanding of chemical bond activation principles in complex enzymatic reaction networks and molecular mechanisms of dioxygenases.

show abstract

Section: Discussionsupporting

confidence: 58%

Peroxy Intermediate Drives Carbon Bond Activation in the Dioxygenase AsqJ

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…Proceeding by a I2M pathway, an electron-withdrawing group on 1 causes destabilization of the Ru V = O species, favoring the O-O bond formation. For catalysts following WNA pathway, Rodriguez et al (2021) reported that increasing electron-withdrawing ability can facilitate the nucleophilic attack at the Ir V intermediate (a rate-determining step), therefore enhance the catalytic activity of [Cp*Ir (Xpic)NO 3 ], as indicated by the correlations between σ and the measured TOF max . Yoshida et al (2010) and Abdel-Magied et al (2017) reported that for single-site Ru complex, a more electron-donating substituent affords a smaller oxidation potential of Ru center and enhances its catalytic activity.…”

Section: C6h4xmentioning

confidence: 99%

“…In addition to aforementioned intermolecular interactions, Timmer et al (2021) discovered that off-set interactions that introduced by de-symmetrization of the axial ligands in complex 16 and 17 (Figure 7A) can provide enough space for the O-O bond formation and reduce reaction barrier. DFT calculations suggested that reduced kinetic barrier of the second-order O-O bond formation ensures high catalytic performance especially at low catalyst concentrations.…”

Section: Off-set Interactionsmentioning

confidence: 99%

“…The steric hindrance inhibits the acceptance of electrons from PS − and impedes the formation of Co(III)-H, a pivotal intermediate for H 2 evolution, from Co(I) (Guo et al, 2021). De Groot and Buda (2021) performed constrained ab initio computational simulations on catalyst-dye supramolecular complex 35 and proved that efficient highperformance dye-sensitized photoelectrochemical cells can be engineered by introducing steric substituents. The properties of partial complexes with different steric hindrance effect are summarized in Table 3.…”

Section: Steric Hindrancementioning

confidence: 99%

“…A faster catalysis was observed by introducing MeO-isoq, which causes a more favorable π—π stacking effects in water ( Richmond et al, 2014 ). Correlated ab initio calculations demonstrated that modulation of π—π stacking dispersion interactions can lower activation barrier, therefore a smaller driving force for the catalysis is obtained ( Johansson et al, 2021 ).…”

Section: Substituent-modification Strategies Of Ligandsmentioning

confidence: 99%

See 2 more Smart Citations

Ligands modification strategies for mononuclear water splitting catalysts

Wang

2022

Front. Chem.

View full text Add to dashboard Cite

Artificial photosynthesis (AP) has been proved to be a promising way of alleviating global climate change and energy crisis. Among various materials for AP, molecular complexes play an important role due to their favorable efficiency, stability, and activity. As a result of its importance, the topic has been extensively reviewed, however, most of them paid attention to the designs and preparations of complexes and their water splitting mechanisms. In fact, ligands design and preparation also play an important role in metal complexes’ properties and catalysis performance. In this review, we focus on the ligands that are suitable for designing mononuclear catalysts for water splitting, providing a coherent discussion at the strategic level because of the availability of various activity studies for the selected complexes. Two main designing strategies for ligands in molecular catalysts, substituents modification and backbone construction, are discussed in detail in terms of their potentials for water splitting catalysts.

show abstract

Off‐Set Interactions of Ruthenium–bda Type Catalysts for Promoting Water‐Splitting Performance

et al. 2021

View full text Add to dashboard Cite

O−O bond formation with Ru(bda)L2‐type catalysts is well‐known to proceed through a bimolecular reaction pathway, limiting the potential application of these catalysts at low concentrations. Herein, we achieved high efficiencies with mononuclear catalysts, with TOFs of 460±32 s−1 at high catalyst loading and 31±3 s−1 at only 1 μM catalyst concentration, by simple structural considerations on the axial ligands. Kinetic and DFT studies show that introduction of an off‐set in the interaction between the two catalytic units reduces the kinetic barrier of the second‐order O−O bond formation, maintaining high catalytic activity even at low catalyst concentrations. The results herein furthermore suggest that π–π interactions may only play a minor role in the observed catalytic activity, and that asymmetry can also rationalize high activity observed for Ru(bda)(isoq)2 type catalysts and offer inspiration to overcome the limitations of 2nd order catalysis.

show abstract

Dispersion forces drive water oxidation in molecular ruthenium catalysts

Abstract: Rational design of artificial water-splitting catalysts is central for developing new sustainable energy technology.

Cited by 5 publications

References 65 publications

Peroxy Intermediate Drives Carbon Bond Activation in the Dioxygenase AsqJ

Peroxy Intermediate Drives Carbon Bond Activation in the Dioxygenase AsqJ

Ligands modification strategies for mononuclear water splitting catalysts

Off‐Set Interactions of Ruthenium–bda Type Catalysts for Promoting Water‐Splitting Performance

Contact Info

Product

Resources

About