1626-00-2Relevant articles and documents
Metal cation-methyl interactions in CB11Me12 - salts of Me3Ge+, Me3Sn +, and Me3Pb+
Zharov, Ilya,Weng, Tsu-Chien,Orendt, Anita M.,Barich, Dewey H.,Penner-Hahn, James,Grant, David M.,Havlas, Zdenek,Michl, Josef
, p. 12033 - 12046 (2004)
Oxidation of Me6M2 (M = Ge, Sn) and Me4Pb with the CB11Me12 radical in alkane solvents produced the insoluble salts Me3M+CB11 Me12, - characterized by CP-MAS NMR and EXAFS. The cations interact with methyl groups of CB11Me12- with coordination strength increasing from Pb to Ge. Density functional theory (DFT) calculations for the isolated ion pairs, Me3M+CB11Me 12- (M = Ge, Sn), revealed three isomers with the cation above methyl 2, 7, or 12, and not above a BB edge or a BBB triangle. The interaction has a considerable covalent component, with the cation attempting to perform a backside SE2 substitution on the methyl carbon. In a fourth less favorable isomer the cation is near methyl 1, inclined toward methyl 2, and interacts with hydrogens. DFT atomic charge distributions and plots of the electrostatic potential on the surface of spheres centered at the CB 11H12 and CB11Me12-, icosahedra display the effects of uneven charge distribution within the anion and contradict the common belief that the negative charge of the cage anion is concentrated primarily on the cage boron atoms 7-12; in CB11Me 12-, roughly half is on the cage carbon and the rest on methyls 7-12.
General access to para-substituted styrenes
Langle, Sandrine,David-Quillot, Franck,Balland, Alexia,Abarbri, Mohamed,Duchêne, Alain
, p. 113 - 119 (2007/10/03)
A simple and efficient procedure has been developed for the synthesis of organogermanium compounds and styrenes para-substituted with groups containing an atom of the 14th group by one-pot reaction of halogenosilanes, germanes or stannanes, organic halides and magnesium using ultrasound methods.
Carbanions as intermediates in the formation of Grignard reagents
Van Klink, Gerard P.M.,De Boer, Henricus J.R.,Schat, Gerrit,Akkerman, Otto S.,Bickelhaupt, Friedrich,Spek, Anthony L.
, p. 2119 - 2135 (2008/10/08)
The formation of reactive carbanions in Grignard reagents was discussed. Inter- and/or intramolecular migrations of organotin and organosilicon groups were also studied. Results showed that the high percentage of rearrangement reactions proves that the anionic species are not located on a minor pathway.
