Cross-Coupling of NHC/CAAC-Based Carbodicarbene: Synthesis of Electron-Deficient Diradicaloids

Herein, we report nickel(0)-catalyzed cross-coupling reactions of NHC/CAAC-based carbodicarbene (NHC = <i>N</i>-heterocyclic carbene and CAAC = cyclic(alkyl)(amino)carbene) with different aryl chlorides, bromides, and iodides. The resulting aryl-substituted cationic carbodicarbene derivatives are prone to one-electron oxidation yielding radical-dications, which, depending on the aryl motif employed, follow different modes of radical-radical dimerization and constitute an entry point to carbon/nitrogen- and nitrogen/nitrogen-centered diradicaloids. Subsequently, this coupling strategy was strategically applied to the synthesis of <i>p</i>-phenylene- and <i>p</i>,<i>p'</i>-biphenylene-bridged carbon/carbon-centered electron-deficient diradicaloids. The employed π-conjugated spacer plays a crucial role in determining the triplet population at room temperature by modulation of the singlet-triplet gap: EPR inactive for <i>p</i>-phenylene vs EPR active for <i>p</i>,<i>p'</i>-biphenylene. Nearly two decades after the disclosure of carbodicarbenes as donor-stabilized atomic carbon equivalents by Tonner and Frenking in 2007, we demonstrate their cross-couplings with a series of aryl halides/dihalides and, based on this, developed a modular methodology for the systematic synthesis of various electron-deficient diradicaloids.