Synthesis and Reactivity of N‑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.