Synthetic, structural, and theoretical investigations of alkali metal germanium hydrides - Contact molecules and separated ions

Weijie Teng, Damian G. Allis, Karin Ruhlandt

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The preparation of a series of crown ether ligated alkali metal (M = K, Rb, Cs) germyl derivatives M(crown ether)nGeH3 through the hydrolysis of the respective tris(trimethylsilyl)germanides is reported. Depending on the alkali metal and the crown ether diameter, the hydrides display either contact molecules or separated ions in the solid state, providing a unique structural insight into the geometry of the obscure GeH3 - ion. Germyl derivatives displaying M-Ge bonds in the solid state are of the general formula [M([18]crown-6)(thf)GeH3] with M = K (1) and M = Rb (4). The compounds display an unexpected geome try with two of the GeH3 hydrogen atoms closely approaching the metal center, resulting in a partially inverted structure. Interestingly, the lone pair at germanium is not pointed towards the alkali metal, rather two of the three hydrides are approaching the alkali metal center to display M-H interactions. Separated ions display alkali metal cations bound to two crown ethers in a sandwich-type arrangement and non-coordinated GeH3- ions to afford complexes of the type [M(crown ether)2]-[GeH3] with M = K, crown ether = [15]crown-5 (2); M = K, crown ether = [12]crown-4 (3); and M = Cs, crown ether = [18]crown-6 (5). The highly reactive germyl derivatives were characterized by using X-ray crystallography, 1H and 13C NMR, and IR spectroscopy. Density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2) calculations were performed to analyze the geometry of the GeH3- ion in the contact molecules 1 and 4.

Original languageEnglish (US)
Pages (from-to)1309-1319
Number of pages11
JournalChemistry - A European Journal
Volume13
Issue number4
DOIs
StatePublished - 2007

Fingerprint

Germanium
Alkali Metals
Crown Ethers
Crown ethers
Alkali metals
Hydrides
Ions
Molecules
Derivatives
Display devices
Geometry
X ray crystallography
Nuclear magnetic resonance spectroscopy
Density functional theory
Cations
Hydrogen
Infrared spectroscopy
Hydrolysis
Positive ions
Metals

Keywords

  • Alkali metals
  • Density functional calculations
  • Germanium
  • Hydrides
  • Structure elucidation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthetic, structural, and theoretical investigations of alkali metal germanium hydrides - Contact molecules and separated ions. / Teng, Weijie; Allis, Damian G.; Ruhlandt, Karin.

In: Chemistry - A European Journal, Vol. 13, No. 4, 2007, p. 1309-1319.

Research output: Contribution to journalArticle

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abstract = "The preparation of a series of crown ether ligated alkali metal (M = K, Rb, Cs) germyl derivatives M(crown ether)nGeH3 through the hydrolysis of the respective tris(trimethylsilyl)germanides is reported. Depending on the alkali metal and the crown ether diameter, the hydrides display either contact molecules or separated ions in the solid state, providing a unique structural insight into the geometry of the obscure GeH3 - ion. Germyl derivatives displaying M-Ge bonds in the solid state are of the general formula [M([18]crown-6)(thf)GeH3] with M = K (1) and M = Rb (4). The compounds display an unexpected geome try with two of the GeH3 hydrogen atoms closely approaching the metal center, resulting in a partially inverted structure. Interestingly, the lone pair at germanium is not pointed towards the alkali metal, rather two of the three hydrides are approaching the alkali metal center to display M-H interactions. Separated ions display alkali metal cations bound to two crown ethers in a sandwich-type arrangement and non-coordinated GeH3- ions to afford complexes of the type [M(crown ether)2]-[GeH3] with M = K, crown ether = [15]crown-5 (2); M = K, crown ether = [12]crown-4 (3); and M = Cs, crown ether = [18]crown-6 (5). The highly reactive germyl derivatives were characterized by using X-ray crystallography, 1H and 13C NMR, and IR spectroscopy. Density functional theory (DFT) and second-order M{\o}ller-Plesset perturbation theory (MP2) calculations were performed to analyze the geometry of the GeH3- ion in the contact molecules 1 and 4.",
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N2 - The preparation of a series of crown ether ligated alkali metal (M = K, Rb, Cs) germyl derivatives M(crown ether)nGeH3 through the hydrolysis of the respective tris(trimethylsilyl)germanides is reported. Depending on the alkali metal and the crown ether diameter, the hydrides display either contact molecules or separated ions in the solid state, providing a unique structural insight into the geometry of the obscure GeH3 - ion. Germyl derivatives displaying M-Ge bonds in the solid state are of the general formula [M([18]crown-6)(thf)GeH3] with M = K (1) and M = Rb (4). The compounds display an unexpected geome try with two of the GeH3 hydrogen atoms closely approaching the metal center, resulting in a partially inverted structure. Interestingly, the lone pair at germanium is not pointed towards the alkali metal, rather two of the three hydrides are approaching the alkali metal center to display M-H interactions. Separated ions display alkali metal cations bound to two crown ethers in a sandwich-type arrangement and non-coordinated GeH3- ions to afford complexes of the type [M(crown ether)2]-[GeH3] with M = K, crown ether = [15]crown-5 (2); M = K, crown ether = [12]crown-4 (3); and M = Cs, crown ether = [18]crown-6 (5). The highly reactive germyl derivatives were characterized by using X-ray crystallography, 1H and 13C NMR, and IR spectroscopy. Density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2) calculations were performed to analyze the geometry of the GeH3- ion in the contact molecules 1 and 4.

AB - The preparation of a series of crown ether ligated alkali metal (M = K, Rb, Cs) germyl derivatives M(crown ether)nGeH3 through the hydrolysis of the respective tris(trimethylsilyl)germanides is reported. Depending on the alkali metal and the crown ether diameter, the hydrides display either contact molecules or separated ions in the solid state, providing a unique structural insight into the geometry of the obscure GeH3 - ion. Germyl derivatives displaying M-Ge bonds in the solid state are of the general formula [M([18]crown-6)(thf)GeH3] with M = K (1) and M = Rb (4). The compounds display an unexpected geome try with two of the GeH3 hydrogen atoms closely approaching the metal center, resulting in a partially inverted structure. Interestingly, the lone pair at germanium is not pointed towards the alkali metal, rather two of the three hydrides are approaching the alkali metal center to display M-H interactions. Separated ions display alkali metal cations bound to two crown ethers in a sandwich-type arrangement and non-coordinated GeH3- ions to afford complexes of the type [M(crown ether)2]-[GeH3] with M = K, crown ether = [15]crown-5 (2); M = K, crown ether = [12]crown-4 (3); and M = Cs, crown ether = [18]crown-6 (5). The highly reactive germyl derivatives were characterized by using X-ray crystallography, 1H and 13C NMR, and IR spectroscopy. Density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2) calculations were performed to analyze the geometry of the GeH3- ion in the contact molecules 1 and 4.

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