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

Abstract

Through the reaction of the aminotroponiminatogermylene monochloride complex [(Bu i 2 ATI)GeCl] ( 1 ) with sodium pyrrolide, the stable N -germylene pyrrole complex [(Bu i 2 ATI)GeNC 4 H 4 ] ( 2 ) has been isolated. The reaction of compound 2 with thiophenol and selenophenol afforded the first germylene thio- and selenophenoxide complexes [(Bu i 2 ATI)GeSPh] ( 3 ) and [(Bu i 2 ATI)GeSePh] ( 4 ) through the substitution of the pyrrole moiety (NC 4 H 4 ) with an EPh moiety (E = S ( 3 ), Se ( 4 )), respectively. Interestingly, the chalcogenide derivatives of compound 2, such as the N -germathioacylpyrrole complex [(Bu i 2 ATI)Ge(S)NC 4 H 4 ] ( 5 ) and N -germaselenoacylpyrrole complex [(Bu i 2 ATI)Ge(Se)NC 4 H 4 ] ( 6 ), also underwent the aforementioned substitution reaction with thiophenol and selenophenol, resulting in the first examples of germa thioester complexes ([(Bu i 2 ATI)Ge(S)SPh] ( 7 ) and [(Bu i 2 ATI)Ge(Se)SPh] ( 8 )) and germa selenoester complexes ([(Bu i 2 ATI)Ge(S)SePh] ( 9 ) and [(Bu i 2 ATI)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 Ge II –S and Ge II –Se bond lengths in compounds 3 and 4 are 2.367(1) and 2.511(1) Å, respectively. The average Ge IV –S and Ge IV –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.