Reactivity of LGe–NR2 and LGe(E)–NR2 over LGe–Cl and LGe(E)–Cl toward Me3SiX (L = Aminotroponiminate; NR2 = N(SiMe3)2/NC4H4; E = S/Se; X = Br/CN)

The halogen exchange reaction of either germylene monochloride [LGeCl] (1) or germachalcogenoacid chlorides [LGe­(E)­Cl] (L = (i-Bu)2ATI; ATI = aminotroponiminate; E = S (V)/Se (VI)) with Me3SiX (X = Br/CN) did not occur. Therefore, the reactions of germanium compounds containing Ge–N bonds with Me3SiBr/CN were tried. Germylene amide [LGeN­(SiMe3)2] (2) reacted with Me3SiBr to afford the aminotroponiminatogermylene monobromide [LGeBr] (3). Similarly, the chalcogen derivatives of compound 2, viz., germachalcogenoamides [LGe­(E)­N­(SiMe3)2] (E = S 4 and Se 5) reacted with Me3SiBr and resulted in germachalcogenoacid bromides [LGe­(E)­Br] (E = S 6 and Se 7), respectively. N-Germylene pyrrole [LGeNC4H4] (2a) and N-germachalcogenoacylpyrroles [LGe­(E)­NC4H4] (E = S 4a, Se 5a) also reacted with Me3SiBr and afforded compounds 3, and 6−7 in excellent yields, respectively. Interestingly, the reaction of compound 2a with Me3SiCN afforded germanium­(II) cyanide [LGeCN] (8). The difference in the reactivity of compounds (1, V, and VI) with Ge–Cl bonds against the compounds (2, 4, and 5) with Ge–N bonds was analyzed theoretically.