Krüger Julia, Wölper Christoph, Schulz Stephan
Institute for Inorganic Chemistry and Center for Nanointegration Duisburg-Essen (Cenide), University of Duisburg-Essen, Universitätsstrasse 5-7, 45117, Essen, Germany.
Angew Chem Int Ed Engl. 2021 Feb 15;60(7):3572-3575. doi: 10.1002/anie.202013618. Epub 2020 Dec 15.
A comprehensive reactivity study of gallapnictenes LGaEGa(Cl)L (E=As, Sb; L=HC[C(Me)N(Ar)] , Ar=Dip=2,6-i-Pr C H ) 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)] E }{IPrH } (E=As 1, Sb 2), and those with HCl and MeI gave pnictanes [LGa(Cl)] 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 ) ][BAr ] (BAr =B(C F ) ) to 5 and 6, while reactions with MeI yielded [LGa(Cl)] EMe (E=As 9, Sb 10). Single electron oxidation reactions of pnictanides 1 and 2 gave the corresponding radicals [LGa(Cl)] E (E=As, Sb).
对镓氮烯LGaEGa(Cl)L（E = As、Sb；L = HC[C(Me)N(Ar)]，Ar = Dip = 2,6 - i - Pr₂C₆H₃）进行的全面反应性研究证明了氮族元素的亲核特性以及Ga原子的亲电性质。LGaEGa(Cl)L与氯化咪唑鎓[IPrH][Cl]反应生成{[LGa(Cl)]₂E}{IPrH₂}（E = As 1，Sb 2），与HCl和MeI反应分别生成氮烷[LGa(Cl)]₂EH（E = As 5，Sb 6）和L(I)GaE(Me)Ga(Cl)L（E = As 7，Sb 8）。氮化物1和2也与[H(OEt₂)][BArF₂⁴]（BArF₂⁴ = B(C₆F₅)₄）反应生成5和6，而与MeI反应生成[LGa(Cl)]₂EMe（E = As 9，Sb 10）。氮化物1和2的单电子氧化反应生成了相应的自由基[LGa(Cl)]₂E（E = As、Sb）。
