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

从π键合镓氮烯到亲核、氧化还原活性金属配位氮烷类化合物

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Abstract

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).

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