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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• 作者：Rahul Kumar Siwatch ; Surendar Karwasara ; Mahendra Kumar Sharma ; Santigopal Mondal ; Goutam Mukherjee ; Gopalan Rajaraman ; Selvarajan Nagendran
• 刊名：Organometallics
• 出版年：2016
• 出版时间：February 22, 2016
• 年：2016
• 卷：35
• 期：4
• 页码：429-438
• 全文大小：477K
• ISSN：1520-6041

文摘

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.