ArticleNature chemistry2013
Redox-inactive metals modulate the reduction potential in heterometallic manganese-oxido clusters.
Article in Nature chemistry, 2013. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 84 papers.
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84 citing papers in PubMed.
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- Activation of the Ground and Excited State of a Luminescent Osmium(VI) Dioxo Dicyano Complex with Lewis Acids.Journal of the American Chemical Society · 2026Article
- Activation of Dioxygen via Neodymium-Alkali Metal Clusters.Journal of the American Chemical Society · 2026Article
- Remote Positioning of Cations Tunes Catalytic Fe-Mediated Nitrogen Fixation Selectivity for Hydrazine Instead of Ammonia in Protic Media.Angewandte Chemie (International ed. in English) · 2026Article
- Alkali Counterion-Dependent Crystallization of Uranium(IV)-Chloro Structural Units.Inorganic chemistry · 2025Article
- Fresh Impetus in the Chemistry of Calcium Peroxides.Journal of the American Chemical Society · 2024Article
- Metal-cation-induced shifts in thiolate redox and reduced sulfur speciation.Chemical science · 2024Article
- Appended Lewis Acids Enable Dioxygen Reactivity and Catalytic Oxidations with Ni(II).Journal of the American Chemical Society · 2024Article
- Long-range electrostatic effects from intramolecular Lewis acid binding influence the redox properties of cobalt-porphyrin complexes.Chemical science · 2024Article
- Current analysis of cations substitution in the oxygen-evolving complex of photosystem II.Biophysical reviews · 2024Review
- Redox Processes Involving Oxygen: The Surprising Influence of Redox-Inactive Lewis Acids.JACS Au · 2024Review
- Formation of a Reactive [Mn(III)-O-Ce(IV)] Species and its Facile Equilibrium with Related Mn(IV)(OX) (X = Sc or H) Complexes.Angewandte Chemie (International ed. in English) · 2024Article
- Structural distortion by alkali metal cations modulates the redox and electronic properties of CeChemical science · 2023Article
- Metal Site-Specific Electrostatic Field Effects on a Tricopper(I) Cluster Probed by Resonant Diffraction Anomalous Fine Structure (DAFS).Inorganic chemistry · 2023Article
- Structural and energetic insights into Mn-to-Fe substitution in the oxygen-evolving complex.iScience · 2023Article
- Redox Potentials of Uranyl Ions in Macrocyclic Complexes: Quantifying the Role of Counter-Ions.ACS omega · 2023Article
- Altering Oxygen Binding by Redox-Inactive Metal Substitution to Control Catalytic Activity: Oxygen Reduction on Manganese Oxide Nanoparticles as a Model System.Angewandte Chemie (International ed. in English) · 2023Article
- Synergistic effects of CHChemical science · 2022Article
- Tunable metal hydroxide-organic frameworks for catalysing oxygen evolution.Nature materials · 2022Article
- Mimicking the Oxygen-Evolving Center in Photosynthesis.Frontiers in plant science · 2022Review
24 more citing papers are in PubMed but not listed here.
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Abstract
Redox-inactive metals are found in biological and heterogeneous water oxidation catalysts, but, at present, their roles in catalysis are not well understood. Here, we report a series of high-oxidation-state tetranuclear-dioxido clusters comprising three manganese centres and a redox-inactive metal (M). Crystallographic studies show an unprecedented Mn3M(µ4-O)(µ2-O) core that remains intact on changing M or the manganese oxidation state. Electrochemical studies reveal that the reduction potentials span a window of 700 mV and are dependent on the Lewis acidity of the second metal. With the pKa of the redox-inactive metal-aqua complex as a measure of Lewis acidity, these compounds demonstrate a linear dependence between reduction potential and acidity with a slope of ∼100 mV per pKa unit. The Sr(2+) and Ca(2+) compounds show similar potentials, an observation that correlates with the behaviour of the oxygen-evolving complex of photosystem II, which is active only if one of these two metals is present.
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