Premium
Designing Stable Radicals with Highly Electrophilic or Nucleophilic Character: Thiadiazinyl as a Case Study
Author(s) -
De Vleeschouwer Freija,
Chankisjijev Artiom,
Geerlings Paul,
De Proft Frank
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201403198
Subject(s) - electrophile , nucleophile , chemistry , radical , computational chemistry , combinatorial chemistry , photochemistry , organic chemistry , catalysis
Theoretical design can be an important aid in the discovery of valuable stable radical systems. In this study, inverse molecular design was applied to thiadiazinyl radicals to maximize two fundamental electronic properties in chemistry, namely electrophilicity and nucleophilicity. We discovered that the thiadiazinyl structure can be made moderately nucleophilic or highly electrophilic, depending on the electronic character of its substituents. The most electrophilic thiadiazinyl radical displays the highest electrophilic character encountered so far for uncharged radical systems. The accumulated data relating to the influence of different substituents at the various sites has allowed us to propose thiadiazinyl radicals that are intrinsically stable and as electrophilic or nucleophilic as possible. Although the nucleophilicity optimum fulfills the additional requirement of being stable, a significant drop from highly to merely moderately electrophilic is observed for the new electrophilicity optimum.