Abstract
AbstractChemists have designed strategies that trigger the conformational isomerization of molecules in response to external stimuli, which can be further applied to regulate the complexation between Lewis acids and bases. We have recently developed a system in which frustrated carbene–borane pairs are revived from shelf-stable but external-stimuli-responsive carbene–borane adducts comprised of N-phosphine-oxide-substituted imidazolylidenes (PoxIms) and triarylboranes. Herein, we report the detailed mechanism on this revival process. A thermally induced borane-transfer process from the carbene carbon atom to the N-phosphinoyl oxygen atom initiates the transformation of the carbene–borane adduct. Subsequent conformational isomerization via the rotation of the N-phosphinoyl group in PoxIm moieties eventually leads to the revival of frustrated carbene–borane pairs that can cleave H2. We believe that this work illustrates an essential role of dynamic conformational isomerization in the regulation of the reactivity of external-stimuli-responsive Lewis acid-base adducts that contain multifunctional substituents.
Funder
MEXT | Japan Society for the Promotion of Science
the Environmental Restoration and Conservation Agency of Japan
Publisher
Springer Science and Business Media LLC
Subject
Materials Chemistry,Biochemistry,Environmental Chemistry,General Chemistry
Cited by
3 articles.
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