Synthesis and Reactivity of <i>N</i>‑Amino­troponiminato­germylene­pyrrole and Its Derivatives

Through the reaction of the amino­troponiminato­germylene monochloride complex [(Bui2ATI)­GeCl] (1) with sodium pyrrolide, the stable N-germylene pyrrole complex [(Bui2ATI)­GeNC4H4] (2) has been isolated. The reaction of compound 2 with thiophenol and selenophenol afforded the first germylene thio- and selenophenoxide complexes [(Bui2ATI)­GeSPh] (3) and [(Bui2ATI)­GeSePh] (4) through the substitution of the pyrrole moiety (NC4H4) with an EPh moiety (E = S (3), Se (4)), respectively. Interestingly, the chalcogenide derivatives of compound 2, such as the N-germathio­acylpyrrole complex [(Bui2ATI)­Ge­(S)­NC4H4] (5) and N-germaseleno­acylpyrrole complex [(Bui2ATI)­Ge­(Se)­NC4H4] (6), also underwent the aforementioned substitution reaction with thiophenol and selenophenol, resulting in the first examples of germa thioester complexes ([(Bui2ATI)­Ge­(S)­SPh] (7) and [(Bui2ATI)­Ge­(Se)­SPh] (8)) and germa selenoester complexes ([(Bui2ATI)­Ge­(S)­SePh] (9) and [(Bui2ATI)­Ge­(Se)­SePh] (10)), respectively. All the novel germanium compounds 3–10 have been unequivocally characterized through multinuclear NMR spectroscopy along with the germylene complex 2. Further, compounds 3–5 and 7–10 were characterized through single-crystal X-ray diffraction studies. The GeII–S and GeII–Se bond lengths in compounds 3 and 4 are 2.367(1) and 2.511(1) Å, respectively. The average GeIV–S and GeIV–Se bond lengths in germa thioester (7 and 8) and germa selenoester (9 and 10) complexes are 2.241(1) and 2.362(1) Å, respectively.通过氨基环庚三烯酮亚胺基锗烯一氯化物配合物[(Bui₂ATI)­GeCl]（化合物1）与吡咯钠的反应，我们成功分离得到了稳定的N-锗烯基吡咯配合物[(Bui₂ATI)­GeNC₄H₄]（化合物2）。 将化合物2分别与苯硫酚和苯硒酚反应，通过以EPh基团（E=S对应化合物3，E=Se对应化合物4）取代吡咯基团（NC₄H₄），首次得到了锗烯基苯硫酚盐配合物[(Bui₂ATI)­GeSPh]（3）和锗烯基苯硒酚盐配合物[(Bui₂ATI)­GeSePh]（4）。 有趣的是，化合物2的硫族元素衍生物——如N-锗代硫酰基吡咯配合物[(Bui₂ATI)­Ge­(S)­NC₄H₄]（5）与N-锗代硒酰基吡咯配合物[(Bui₂ATI)­Ge­(Se)­NC₄H₄]（6）——同样可与苯硫酚和苯硒酚发生上述取代反应，分别得到首例锗代硫酯配合物([(Bui₂ATI)­Ge­(S)­SPh]（7）和[(Bui₂ATI)­Ge­(Se)­SPh]（8）)与锗代硒酯配合物([(Bui₂ATI)­Ge­(S)­SePh]（9）和[(Bui₂ATI)­Ge­(Se)­SePh]（10）)。 所有新型锗化合物3~10以及锗烯配合物2均通过多核核磁共振波谱法得到了明确的结构表征。进一步地，化合物3~5与7~10还通过单晶X射线衍射实验完成了结构解析。 化合物3与4中的Ge(II)–S键与Ge(II)–Se键键长分别为2.367(1) Å和2.511(1) Å。锗代硫酯（7、8）与锗代硒酯（9、10）配合物中的平均Ge(IV)–S键与Ge(IV)–Se键键长分别为2.241(1) Å和2.362(1) Å。