Synthesis, structure and bonding nature of heavy dipnictene radical anions

Abstract

Cyclic voltammetry (CV) studies of two L(X)Ga-substituted dipnictenes [L(R₂N)GaE]₂ (E = Sb, R = Me 1; E = Bi; R = Et 2; L = HC[C(Me)NDipp]₂; Dipp = 2,6-i-Pr₂C₆H₃) showed reversible reduction events. Single electron reduction of 1 and 2 with KC₈ in DME in the presence of benzo-18-crown-6 (B-18-C-6) gave the corresponding dipnictenyl radical anions (DME)[K(B-18-C-6)][L(R₂N)GaE]₂ (E = Sb, R = Me 3; E = Bi, R = Et 4). Radical anions 3 and 4 were characterized by EPR, UV-vis and single crystal X-ray diffraction, while quantum chemical calculations gave deeper insight into the nature of the chemical bonding.