NOPR - NISCAIR Online Periodicals Repository
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Title |
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)
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Abstract |
The halogen exchange reaction of either germylene monochloride [LGeCl] (1) or germachalcogenoacid chlorides [LGe(E)Cl] (L = (i-Bu)(2)ATI; 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.
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N-HETEROCYCLIC GERMYLENES
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ORGANOMETALLICS,35(4)429-438
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