Isolation and Structure of Germylene‐Germyliumylidenes Stabilized by N‐Heterocyclic Imines

The ditopic germanium complex FGe(NIPr) 2 Ge[BF 4 ] ( 3 [BF 4 ]; IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) is prepared by the reaction of the amino(imino)germylene (Me 3 Si) 2 NGeNIPr ( 1 ) with BF 3 ⋅OEt 2 . This monocation is converted into the germylene‐germyliumylidene 3 [BAr F 4 ] [Ar F =3,5‐(CF 3 ) 2 ‐C 6 H 3 ] by treatment with Na[BAr F 4 ]. The tetrafluoroborate salt 3 [BF 4 ] reacts with 2 equivalents of Me 3 SiOTf to give the novel complex (OTf)(GeNIPr) 2 [OTf] ( 4 [OTf]), which affords 4 [BAr F 4 ] and 4 [Al(OR F ) 4 ] [R F =C(CF 3 ) 3 ] after anion exchange with Na[BAr F 4 ] or Ag[Al(OR F ) 4 ], respectively. The computational, as well as crystallographic study, reveals that 4 + has significant bis(germyliumylidene) dication character.