Crystalline Anions Based on Classical N-Heterocyclic Carbenes

Herein, the first stable anions K[SIPr^Bp ] (4 a-K) and K[IPr^Bp ] (4 b-K) (SIPr^Bp =BpC{N(Dipp)CH₂ }₂ , IPr^Bp =BpC{N(Dipp)CH}₂ ; Bp=4-PhC₆ H₄ ; Dipp=2,6-iPr₂ C₆ H₃ ) derived from classical N-heterocyclic carbenes (NHCs) (i.e. SIPr and IPr) have been isolated as violet crystalline solids. 4 a-K and 4 b-K are prepared by KC₈ reduction of the neutral radicals [SIPr^Bp ] (3 a) and [IPr^Bp ] (3 b), respectively. The radicals 3 a and 3 b as well as [Me-IPr^Bp ] 3 c (Me-IPr^Bp =BpC{N(Dipp)CMe}₂ ) are accessible as crystalline solids on treatment of the respective 1,3-imidazoli(ni)um bromides (SIPr^Bp )Br (2 a), (IPr^Bp )Br (2 b), and (Me-IPr^Bp )Br (2 c) with KC₈ . The cyclic voltammograms of 2 a-2 c exhibit two one-electron reversible redox processes in -0.5 to -2.5 V region that correspond to the radicals 3 a-3 c and the anions (4 a-4 c)^- . Computational calculations suggest a closed-shell singlet ground state for (4 a-4 c)^- with the singlet-triplet energy gap of 17-24 kcal mol^-1 .