TY - JOUR
T1 - Syntheses and structures of the first heavy-alkali-metal tris(trimethylsilyl)germanides
AU - Teng, Weijie
AU - Ruhlandt-Senge, Karin
PY - 2005/4/8
Y1 - 2005/4/8
N2 - 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(SiMe3)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 29Si NMR spectroscopic studies. Here we report on two series of germanides, one displaying M-Ge bonds in the solid state with the general formula [M(donor)nGe(SiMe3)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(SiMe3)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 com pounds are highly sensitive towards hydrolysis, use of the tridentate nitrogen donor PMDTA (PMDTA = N,N,N′,N′,N′- pentamethyldiethylene-triamine) afforded even more reactive species of the composition [K(pmdta)2-Ge(SiMe3)3] (8). We also include the silanide analogue [K(pmdta)2Si(SiMe3) 3] (9) for sake of comparison. The compounds were typically characterized by X-ray crystallography, and 1H, 13C, and 29Si NMR and IR spectroscopy, unless extremely high reactivity, as observed for the PMDTA adducts 8 and 9, prevented a more detailed characterization.
AB - 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(SiMe3)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 29Si NMR spectroscopic studies. Here we report on two series of germanides, one displaying M-Ge bonds in the solid state with the general formula [M(donor)nGe(SiMe3)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(SiMe3)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 com pounds are highly sensitive towards hydrolysis, use of the tridentate nitrogen donor PMDTA (PMDTA = N,N,N′,N′,N′- pentamethyldiethylene-triamine) afforded even more reactive species of the composition [K(pmdta)2-Ge(SiMe3)3] (8). We also include the silanide analogue [K(pmdta)2Si(SiMe3) 3] (9) for sake of comparison. The compounds were typically characterized by X-ray crystallography, and 1H, 13C, and 29Si NMR and IR spectroscopy, unless extremely high reactivity, as observed for the PMDTA adducts 8 and 9, prevented a more detailed characterization.
KW - Alkali metals
KW - Germanium
KW - Ion association
KW - Metathesis
KW - Structure elucidation
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U2 - 10.1002/chem.200400810
DO - 10.1002/chem.200400810
M3 - Article
C2 - 15696585
AN - SCOPUS:17444430431
SN - 0947-6539
VL - 11
SP - 2462
EP - 2470
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 8
ER -