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Title: Tuning Reactivity and Electronic Properties through Ligand Reorganization within a Cerium Heterobimetallic Framework

Cerium compounds have played vital roles in organic, inorganic, and materials chemistry due to their reversible redox chemistry between trivalent and tetravalent oxidation states. However, attempts to rationally access molecular cerium complexes in both oxidation states have been frustrated by unpredictable reactivity in cerium(III) oxidation chemistry. Such oxidation reactions are limited by steric saturation at the metal ion, which can result in high energy activation barriers for electron transfer. An alternative approach has been realized using a rare earth/alkali metal/1,1'-BINOLate (REMB) heterobimetallic framework, which uses redox-inactive metals within the secondary coordination sphere to control ligand reorganization. The rational syntheses of functionalized cerium(IV) products and a mechanistic examination of the role of ligand reorganization in cerium(III) oxidation are presented.
Authors:
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Publication Date:
OSTI Identifier:
1163962
Report Number(s):
LBNL-6687E
DOE Contract Number:
DE-AC02-05CH11231
Resource Type:
Journal Article
Resource Relation:
Journal Name: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY; Journal Volume: 135; Journal Issue: 50; Related Information: Journal Publication Date: 19016
Research Org:
Ernest Orlando Lawrence Berkeley National Laboratory, Berkeley, CA (US)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY 2,2-DISUBSTITUTED TERMINAL EPOXIDES; WATER-OXIDATION CATALYSTS; INNER-SPHERE MECHANISMS; RAY CRYSTAL-STRUCTURES; GAS-SHIFT REACTION; OUTER-SPHERE; TETRAVALENT CERIUM; METAL-COMPLEXES; LEWIS ACIDITY; SOLID-STATE