Syntheses and structures of the first heavy-alkali-metal tris(trimethylsilyl)germanides

Weijie Teng, Karin Ruhlandt

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

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.

Original languageEnglish (US)
Pages (from-to)2462-2470
Number of pages9
JournalChemistry - A European Journal
Volume11
Issue number8
DOIs
StatePublished - Apr 8 2005

Fingerprint

Alkali Metals
Alkali metals
Heavy metals
Crown ethers
X ray crystallography
Ions
Nuclear magnetic resonance spectroscopy
Crown Ethers
Infrared spectroscopy
Hydrolysis
Nuclear magnetic resonance
Silicon
Nitrogen
Chemical analysis
phenyllithium
18-crown-6

Keywords

  • Alkali metals
  • Germanium
  • Ion association
  • Metathesis
  • Structure elucidation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Syntheses and structures of the first heavy-alkali-metal tris(trimethylsilyl)germanides. / Teng, Weijie; Ruhlandt, Karin.

In: Chemistry - A European Journal, Vol. 11, No. 8, 08.04.2005, p. 2462-2470.

Research output: Contribution to journalArticle

@article{06abc2e571aa4f19be0620fe7e903bd8,
title = "Syntheses and structures of the first heavy-alkali-metal tris(trimethylsilyl)germanides",
abstract = "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.",
keywords = "Alkali metals, Germanium, Ion association, Metathesis, Structure elucidation",
author = "Weijie Teng and Karin Ruhlandt",
year = "2005",
month = "4",
day = "8",
doi = "10.1002/chem.200400810",
language = "English (US)",
volume = "11",
pages = "2462--2470",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "8",

}

TY - JOUR

T1 - Syntheses and structures of the first heavy-alkali-metal tris(trimethylsilyl)germanides

AU - Teng, Weijie

AU - Ruhlandt, 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

UR - http://www.scopus.com/inward/record.url?scp=17444430431&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=17444430431&partnerID=8YFLogxK

U2 - 10.1002/chem.200400810

DO - 10.1002/chem.200400810

M3 - Article

VL - 11

SP - 2462

EP - 2470

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 8

ER -