Heavier Chalcogenoketyl Radical Anions: Synthesis, Characterization and Reactivity

Basic data for this project

Description

Ketyl radical anions [R2CO]∙− are a class of organic radicals that are most commonly generated by SET reductions from their ketone analogues. Ketyls play an indispensable role in chemical synthesis and as (bio-)chemical intermediates. Gaining access to stable heavier chalcogenoketyl radical anions of the type [R2CX]∙− (X = S, Se, Te) and exploring their properties offers valuable insights into the fundamental nature of these highly reactive species while also unlocking their potential for practical applications. However, in contrast to their lighter homologous, the isolation and characterization of heavier chalcogenoketyl radical anions remains elusive. This proposal aims to bridge the gap in chemical literature by isolating, characterizing, and investigating the reactivity of heavier chalcogenoketyl radicals, thereby enhancing our understanding of fundamental periodic trends. Given the anticipated high reactivity and lability of the heavier chalcogeno-ketyl radical anions, extensive steric and/or electronic stabilization will be strategically employed to enable the successful isolation of stable species. The synthetic approach outlined in this proposal aims to establish a "toolbox principle," facilitating a highly systematic modulation of steric and electronic influencing factors exerted by the stabilizing ligands. The in-depth insights into structure–reactivity relationships acquired throughout this work are expected to enable the precise modulation of key molecular parameters, including e.g. the spin density/distribution, and the counterion coordination. Ultimately, this knowledge should facilitate the deliberate fine-tuning of the reactivity of the proposed radical anions, allowing for their targeted modification based on the specific requirements of given synthetic applications.