The role of dynamic ligand exchange in the oxidation chemistry of cerium(iii)

Chemical Science
Jerome R RobinsonEric J Schelter

Abstract

The CeIII/IV couple is useful for many applications in organic, inorganic, and materials chemistry. However, attaining a general method to access both oxidations states through reversible solution redox chemistry remains challenging. Herein we report the synthesis, characterization, and oxidation chemistry of the novel Ce/Li REMB heterochiral diastereomer, 1-Ce(het). The solution exchange processes of 1-RE(het) (RE = Ce and Yb) were investigated to estimate rates of ligand and cation exchange relevant in homochiral and heterochiral frameworks. A detailed mechanistic investigation following the solution dynamics of 1-Ce(het) revealed reactivity controlled both by ligand reorganization and redistribution processes. Ligand reorganization was responsible for the kinetics associated with the chemical oxidation reaction, whereas ligand redistribution and exchange dictated the isolated products.

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Citations

Sep 6, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Grace B PanettiEric J Schelter
Nov 14, 2018·Chemistry : a European Journal·Kirill Nikitin, Ryan O'Gara
Dec 21, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiaoqing Xin, Congqing Zhu
Dec 17, 2019·Angewandte Chemie·Aurélien R WillauerMarinella Mazzanti
Jul 13, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Jochen FriedrichReiner Anwander
Aug 12, 2017·Chemistry : a European Journal·Alexander V ZabulaEric J Schelter
Nov 4, 2020·Chemical Communications : Chem Comm·Min DengGaël Ung
Sep 24, 2020·Chemistry : a European Journal·Moya A Hay, Colette Boskovic
May 21, 2021·Accounts of Chemical Research·Grace B PanettiPatrick J Walsh
Jun 14, 2019·Journal of the American Chemical Society·Chad T PalumboMarinella Mazzanti
Sep 29, 2020·Inorganic Chemistry·Kerry C CaseyJerome R Robinson
Jul 3, 2020·Inorganic Chemistry·Christopher M KotykLinda H Doerrer
Sep 11, 2019·Inorganic Chemistry·Hayato TsurugiKazushi Mashima
Oct 26, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Molly M MacInnesPing Yang

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Methods Mentioned

BETA
X-ray
NMR

Software Mentioned

REMB

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