The role of uranium-arene bonding in H2O reduction catalysis

Beitrag in einer Fachzeitschrift


Details zur Publikation

Autor(en): Halter D, Heinemann F, Maron L, Meyer K
Zeitschrift: Nature Chemistry
Jahr der Veröffentlichung: 2018
Band: 10
Seitenbereich: 259-267
ISSN: 1755-4330
Sprache: Englisch


Abstract

The reactivity of uranium compounds towards small molecules typically
occurs through stoichiometric rather than catalytic processes. Examples
of uranium catalysts reacting with water are particularly scarce,
because stable uranyl groups form that preclude the recovery of the
uranium compound. Recently, however, an arene-anchored, electron-rich
uranium complex has been shown to facilitate the electrocatalytic
formation of H2 from H2O. Here, we present the precise role of uranium–arene δ bonding in intermediates of the catalytic cycle, as well as details of the atypical two-electron oxidative addition of H2O
to the trivalent uranium catalyst. Both aspects were explored by
synthesizing mid- and high-valent uranium–oxo intermediates and by
performing comparative studies with a structurally related complex that
cannot engage in δ bonding. The redox activity of the arene anchor and a covalent δ-bonding interaction with the uranium ion during H2
formation were supported by density functional theory analysis.
Detailed insight into this catalytic system may inspire the design of
ligands for new uranium catalysts.


FAU-Autoren / FAU-Herausgeber

Halter, Dominik
Lehrstuhl für Anorganische und Allgemeine Chemie
Heinemann, Frank Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie
Meyer, Karsten Prof. Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie


Autor(en) der externen Einrichtung(en)
University of Toulouse


Zitierweisen

APA:
Halter, D., Heinemann, F., Maron, L., & Meyer, K. (2018). The role of uranium-arene bonding in H2O reduction catalysis. Nature Chemistry, 10, 259-267. https://dx.doi.org/10.1038/nchem.2899

MLA:
Halter, Dominik, et al. "The role of uranium-arene bonding in H2O reduction catalysis." Nature Chemistry 10 (2018): 259-267.

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Zuletzt aktualisiert 2019-06-01 um 01:10