Litcius/Paper detail

Potassium Aluminyl Promoted Carbonylation of Ethene

Matthew J. Evans, Samuel E. Neale, Mathew D. Anker, Claire L. McMullin, Martyn P. Coles

2022Angewandte Chemie International Edition36 citationsDOIOpen Access PDF

Abstract

Abstract The potassium aluminyl [K{Al(NON Dipp )}] 2 ([NON Dipp ] 2− =[O{SiMe 2 NDipp} 2 ] 2− , Dipp=2,6‐ i Pr 2 C 6 H 3 ) activates ethene towards carbonylation with CO under mild conditions. An isolated bis‐aluminacyclopropane compound reacted with CO via carbonylation of an Al−C bond, followed by an intramolecular hydrogen shift to form K 2 [Al(NON Dipp )( μ ‐CH 2 CH=CO‐1κ 2 C 1,3 ‐2κ O )Al(NON Dipp )Et]. Restricting the chemistry to a mono‐aluminium system allowed isolation of [Al(NON Dipp )(CH 2 CH 2 CO‐κ 2 C 1,3 )] − , which undergoes thermal isomerisation to form the [Al(NON Dipp )(CH 2 CH=CHO‐κ 2 C , O )] − anion. DFT calculations highlight the stabilising influence of incorporated benzene at multiple steps in the reaction pathways.

Topics & Concepts

CarbonylationChemistryIsomerizationIntramolecular forceMedicinal chemistryPotassiumBenzeneCatalysisStereochemistryOrganic chemistryCarbon monoxideSynthesis and characterization of novel inorganic/organometallic compoundsOrganoboron and organosilicon chemistryOrganometallic Complex Synthesis and Catalysis