Crystallographic evidence for a continuum and reversal of roles in primary-secondary interactions in antimony Lewis acids: applications in carbonyl activation

Sharma, D and Benny, A and Gupta, R and Jemmis, ED and Venugopal, A (2022) Crystallographic evidence for a continuum and reversal of roles in primary-secondary interactions in antimony Lewis acids: applications in carbonyl activation. In: Chemical Communications .

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Abstract

Primary and secondary interactions form the basis of substrate activation in Lewis-acid mediated catalysis, with most substrate activations occurring at the secondary binding site. We explore two series of antimony cations, (NMe2CH2C6H4)(mesityl)Sb+ (A) and (NMe2C6H4)(mesityl)Sb+ (B), by coordinating ligands with varying nucleophilicity at the position trans to the N-donor. The decreased nucleophilicity of the incoming ligands leads to reversal from a primary bond to a secondary interaction in A, whereas a constrained N-coordination in B diminishes the border between primary and secondary bonding. Investigations on carbonyl olefin metathesis reactions and carbonyl reduction demonstrate increased reactivity of a Lewis acid when the substrate activation occurs at the primary binding site.

Item Type:	Journal Article
Publication:	Chemical Communications
Publisher:	Royal Society of Chemistry
Additional Information:	The copyright for this article belongs to Royal Society of Chemistry.
Keywords:	alkene; antimony; cation; Lewis acid; ligand, Alkenes; Antimony; Cations; Lewis Acids; Ligands
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	31 Oct 2022 09:26
Last Modified:	31 Oct 2022 09:26
URI:	https://eprints.iisc.ac.in/id/eprint/77673

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