Document Type
Journal Article
Date of this Version
3-22-2016
Publication Source
Chemical Science
Volume
7
Start Page
4537
Last Page
4547
DOI
10.1039/C5SC04897D
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 ¼ 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
Copyright/Permission Statement
This article is published under a CC BY-NC 3.0 license (https://creativecommons.org/licenses/by-nc/3.0)
Recommended Citation
Robinson, J. R., Qiao, Y., Gu, J., Carroll, P. J., Walsh, P. J., & Schelter, E. J. (2016). The Role of Dynamic Ligand Exchange in the Oxidation Chemistry of Cerium(III). Chemical Science, 7 4537-4547. http://dx.doi.org/10.1039/C5SC04897D
Embargo Date
3-24-2017
Date Posted: 10 January 2017
This document has been peer reviewed.