644988-98-7Relevant articles and documents
Synthesis and reactivity of the bulky germanium(IV) trisamide complexes BrGe[N(SiMe3)2]3 and LiGe[N(SiMe 3)2]3: X-ray crystal structures of BrGe[N(SiMe3)2]3 and [(Me3Si) 2N]3Ge(CH2CH2CH2CH 3)
Walding, Jennifer L.,Fanwick, Phillip E.,Weinert, Charles S.
, p. 1186 - 1192 (2005)
The bulky germanium(IV) trisamide complex BrGe[N(SiMe3) 2]3 has been prepared and structurally characterized. Reaction of this material with nBuLi resulted in [(Me 3Si)2N]3Ge(CH2CH2CH 2CH3), which has also been structurally characterized, but no reaction with lithium metal was observed in the attempted preparation of LiGe[N(SiMe3)2]3. However, analytically pure LiGe[N(SiMe3)2]3was prepared by the reaction of 3 equivalents of LiN(SiMe3)2 with GeI2. Evidence is presented that this germyllithium reagent is a major by-product in the synthesis of Ge[N(SiMe3)2]2 when the latter reagent is obtained from GeCl2 ? (dioxane) prepared by the method of Kolesnikov et al. Reaction of the germyllithium reagent with 2,6-diphenylphenol yields the mixed Ge/Li cage complex [Li(μ2- OC6H3Ph2-2,6)3Ge], which had originally been obtained serendipitously via the reaction of 2,6-diphenylphenol with Ge[N(SiMe3)]2.
Synthesis and structures of the group 1 metal/germanium cage complexes [M(μ-OC6H3Ph2-2,6)3Ge] (M = Li, Na, K, Rb, Cs); periodic trends and alkali metal dependent arene bonding
Weinert, Charles S.,Fanvvick, Phillip E.,Rothwell, Ian P.
, p. 1795 - 1802 (2007/10/03)
Reaction of three equivalents of the alkali salts of 2,6-diphenylphenoxide, [MOC6H3Ph2-2,6] (M = Li, Na, K, Rb, Cs) with GeI2 provides the corresponding cage complexes [M(μ-OC 6H3Ph2-2,6)3Ge], all of which have been structurally characterized. These species contain a germanium(II) metal and an alkali metal connected by the oxygen atoms of the bridging aryloxide ligands. The two metal atoms are at the apices of a five-atom trigonal bipyramidal metal framework. The alkali cations are also bound to the carbon atoms of three of the 2,6-diphenyl substitutents of the aryloxide ligands. The number of bonds to these arene rings is strongly dependent on the identity of the alkali metal. This results in high formal coordination numbers for the group 1 metals K, Rb and Cs. The germanium and alkali metal form similar bonds to all three aryloxide oxygens except in the case of the caesium compound. In this case some localization of bonding occurs with structural parameters more consistent with a caesium aryloxide adduct of a germanium(II) bis(aryloxide). The Royal Society of Chemistry 2003.
