TY - JOUR
T1 - Synthetic, structural, and theoretical investigations of alkali metal germanium hydrides - Contact molecules and separated ions
AU - Teng, Weijie
AU - Allis, Damian G.
AU - Ruhlandt-Senge, Karin
PY - 2007
Y1 - 2007
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.
KW - Alkali metals
KW - Density functional calculations
KW - Germanium
KW - Hydrides
KW - Structure elucidation
UR - http://www.scopus.com/inward/record.url?scp=33846622851&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33846622851&partnerID=8YFLogxK
U2 - 10.1002/chem.200601073
DO - 10.1002/chem.200601073
M3 - Article
C2 - 17133638
AN - SCOPUS:33846622851
SN - 0947-6539
VL - 13
SP - 1309
EP - 1319
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 4
ER -