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.
展开▼
机译：Ce III / IV 对可用于有机，无机和材料化学中的许多应用。然而，通过可逆溶液氧化还原化学方法获得进入两种氧化态的通用方法仍然具有挑战性。本文中，我们报告了新型Ce / Li REMB杂手性非对映异构体> 1-Ce（het）的合成，表征和氧化化学。研究了> 1-RE（het）（RE = Ce和Yb）的溶液交换过程，以估计在同手性和杂手性骨架中相关配体和阳离子交换的速率。根据> 1-Ce（het）的溶液动力学进行的详细机理研究表明，反应性受配体重组和再分布过程的控制。配体重组负责与化学氧化反应相关的动力学，而配体的重新分布和交换决定了分离出的产物。
展开▼
