Syntheses and Structures of the First Heavy‐Alkali‐Metal Tris(trimethylsilyl)germanides

The first heavy‐alkali‐metal tris(trimethylsilyl)germanides were obtained in high yield and purity by a simple one‐pot reaction involving the treatment of tetrakis(trimethylsilyl)germane, Ge(SiMe 3 ) 4 , with various alkali metal tert ‐butoxides. The addition of different sizes of crown ethers or the bidentate TMEDA (TMEDA= N , N , N ′, N ′‐tetramethylethylenediamine) provided either contact or separated species in the solid state, whereas in aromatic solvents the germanides dissociate into separated ions, as shown by 29 Si NMR spectroscopic studies. Here we report on two series of germanides, one displaying MGe bonds in the solid state with the general formula [M(donor) n Ge(SiMe 3 ) 3 ] (M=K, donor=[18]crown‐6, n =1, 1 ; Rb, donor=[18]crown‐6, n =1, 4 ; and M=K, donor=TMEDA, n =2, 6 ). The silicon analogue of 6 , [K(tmeda) 2 Si(SiMe 3 ) 3 ] ( 7 ) is also included to provide a point of reference. The second group of compounds consists of separated ions with the general formula [M(donor) 2 ][Ge(SiMe 3 ) 3 ] (M=K, donor=[15]crown‐5, 2 ; M=K, donor=[12]crown‐4, 3 ; and M=Cs, donor=[18]crown‐6, 5 ). While all target compounds are highly sensitive towards hydrolysis, use of the tridentate nitrogen donor PMDTA (PMDTA= N , N , N ′, N ′′, N ′′‐pentamethyldiethylenetriamine) afforded even more reactive species of the composition [K(pmdta) 2 Ge(SiMe 3 ) 3 ] ( 8 ). We also include the silanide analogue [K(pmdta) 2 Si(SiMe 3 ) 3 ] ( 9 ) for sake of comparison. The compounds were typically characterized by X‐ray crystallography, and 1 H, 13 C, and 29 Si NMR and IR spectroscopy, unless extremely high reactivity, as observed for the PMDTA adducts 8 and 9 , prevented a more detailed characterization.