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Taming the Lewis Superacidity of Non‐Planar Boranes: C−H Bond Activation and Non‐Classical Binding Modes at Boron

Arnaud Osi, Damien Mahaut, Nikolay Tumanov, Luca Fusaro, Johan Wouters, Benoı̂t Champagne, Aurélien Chardon, Guillaume Berionni

2021Angewandte Chemie International Edition51 citationsDOI

Abstract

Abstract The rational design of a geometrically constrained boron Lewis superacid featuring exceptional structure and reactivity is disclosed. It enabled the formation of non‐classical electron deficient B−H−B type of bonding, which was supported by spectroscopic and structural parameters as well as computational studies. Taming the pyramidal Lewis acid electrophilicity through weak coordinating anion dissociation enabled a series of highly challenging chemical transformations, such as Csp 2 −H and Csp 3 −H activation under a frustrated Lewis pair regime and the cleavage of Csp 3 −Si bonds. The demonstration of such rich chemical behaviour and flexibility on a single molecular compound makes it a unique mediator of chemical transformations generally restricted to transition metals.

Topics & Concepts

BoranesLewis acids and basesElectrophileChemistryBoronSuperacidComputational chemistryChemical bondFrustrated Lewis pairCrystallographyReactivity (psychology)StereochemistryDissociation (chemistry)Organic chemistryCatalysisAlternative medicineMedicinePathologyOrganoboron and organosilicon chemistryCoordination Chemistry and OrganometallicsSynthesis and characterization of novel inorganic/organometallic compounds
Taming the Lewis Superacidity of Non‐Planar Boranes: C−H Bond Activation and Non‐Classical Binding Modes at Boron | Litcius