Stereo‐ and Regiochemical Effect of <i>N,N</i>‐Dialkylamide Extractants on the Speciation of Pu Complexes

Abstract The relationship between extractant stereochemistry and their extraction performance has only poorly been established. In order to address a part of this concern, we investigated the Pu(IV) liquid‐liquid (LLE) by using N , ‐di‐(2‐ethylhexyl)butyramide (DEHBA), as well those its position isomers. DEHBA ( ββ ‐isomer) ‐(2‐ethylhexyl)‐ ‐(oct‐3‐yl)butyramide (EHOBA or αβ were synthesized mixture stereoisomer stereoenriched R S ) ‐ )‐diastereoisomers, all assessed for Pu IV LLE. results showed that both stereoisomerism aliphatic substituents affect complexation extraction. We found is lowered factor 2 4 when ethyl branching group closer complexing site. UV‐vis spectroscopy decrease was affected steric hindrance inducing deprivation inner sphere complex. Effect highlighted site α ‐position). Enantiopure stereoisomers provided similar extraction, whereas slight could be noticed more cluttered )‐isomers, which also concomitant with smaller population contrast, led strong because an antagonistic association in mixed complexes.