From π‐Bonded Gallapnictenes to Nucleophilic, Redox‐Active Metal‐Coordinated Pnictanides

A comprehensive reactivity study of gallapnictenes LGaEGa(Cl)L (E=As, Sb; L=HC[C(Me)N(Ar)](2), Ar=Dip=2,6‐i‐Pr(2)C(6)H(3)) proved the nucleophilic character of the pnictogen and the electrophilic nature of the Ga atom. Reactions of LGaEGa(Cl)L with imidazolium chloride [IPrH][Cl] yielded {[LGa(Cl)](2)E(−)}{IPrH(+)} (E=As 1, Sb 2), and those with HCl and MeI gave pnictanes [LGa(Cl)](2)EH (E=As 5, Sb 6) and L(I)GaE(Me)Ga(Cl)L (E=As 7, Sb 8). Pnictanides 1 and 2 also react with [H(OEt(2))(2)][BAr(F) (4)] (BAr(F) (4)=B(C(6)F(5))(4)) to 5 and 6, while reactions with MeI yielded [LGa(Cl)](2)EMe (E=As 9, Sb 10). Single electron oxidation reactions of pnictanides 1 and 2 gave the corresponding radicals [LGa(Cl)](2)E(.) (E=As, Sb).