Robinson Jerome R, Qiao Yusen, Gu Jun, Carroll Patrick J, Walsh Patrick J, Schelter Eric J
P. Roy and Diana T. Vagelos Laboratories , Department of Chemistry , University of Pennsylvania , Philadelphia , PA 19104 , USA . Email:
Chem Sci. 2016 Jul 1;7(7):4537-4547. doi: 10.1039/c5sc04897d. Epub 2016 Mar 23.
The Ce 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, . The solution exchange processes of (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 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.
铈（Ce）配合物在有机、无机和材料化学的许多应用中都很有用。然而，通过可逆溶液氧化还原化学获得两种氧化态的通用方法仍然具有挑战性。在此，我们报告了新型Ce/Li REMB异手性非对映异构体的合成、表征及氧化化学。研究了（RE = Ce和Yb）的溶液交换过程，以估计在手性和异手性框架中相关的配体和阳离子交换速率。对溶液动力学进行详细的机理研究后发现，反应活性受配体重组和再分配过程控制。配体重组决定了与化学氧化反应相关的动力学，而配体再分配和交换则决定了分离产物。
