Issue 7, 2016

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

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
18 Dec 2015
Accepted
22 Mar 2016
First published
23 Mar 2016
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2016,7, 4537-4547

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

J. R. Robinson, Y. Qiao, J. Gu, P. J. Carroll, P. J. Walsh and E. J. Schelter, Chem. Sci., 2016, 7, 4537 DOI: 10.1039/C5SC04897D

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