Redox Processes Involving Oxygen: The Surprising Influence of Redox-Inactive Lewis Acids.

Autor: Lionetti D; Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 127-72, Pasadena, California 91125, United States., Suseno S; Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 127-72, Pasadena, California 91125, United States., Shiau AA; Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 127-72, Pasadena, California 91125, United States., de Ruiter G; Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 127-72, Pasadena, California 91125, United States., Agapie T; Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 127-72, Pasadena, California 91125, United States.
Jazyk: angličtina
Zdroj: JACS Au [JACS Au] 2024 Jan 22; Vol. 4 (2), pp. 344-368. Date of Electronic Publication: 2024 Jan 22 (Print Publication: 2024).
DOI: 10.1021/jacsau.3c00675
Abstrakt: Metalloenzymes with heteromultimetallic active sites perform chemical reactions that control several biogeochemical cycles. Transformations catalyzed by such enzymes include dioxygen generation and reduction, dinitrogen reduction, and carbon dioxide reduction-instrumental transformations for progress in the context of artificial photosynthesis and sustainable fertilizer production. While the roles of the respective metals are of interest in all these enzymatic transformations, they share a common factor in the transfer of one or multiple redox equivalents. In light of this feature, it is surprising to find that incorporation of redox- inactive metals into the active site of such an enzyme is critical to its function. To illustrate, the presence of a redox-inactive Ca 2+ center is crucial in the Oxygen Evolving Complex, and yet particularly intriguing given that the transformation catalyzed by this cluster is a redox process involving four electrons. Therefore, the effects of redox inactive metals on redox processes-electron transfer, oxygen- and hydrogen-atom transfer, and O-O bond cleavage and formation reactions-mediated by transition metals have been studied extensively. Significant effects of redox inactive metals have been observed on these redox transformations; linear free energy correlations between Lewis acidity and the redox properties of synthetic model complexes are observed for several reactions. In this Perspective, these effects and their relevance to multielectron processes will be discussed.
Competing Interests: The authors declare no competing financial interest.
(© 2024 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE