Metal cation-methyl interactions in CB11Me12(-) salts of Me3Ge+, Me3Sn+, and Me3Pb+

Journal of the American Chemical Society
Ilya ZharovJosef Michl

Abstract

Oxidation of Me(6)M(2) (M = Ge, Sn) and Me(4)Pb with the CB(11)Me(12)(*) radical in alkane solvents produced the insoluble salts Me(3)M(+)CB(11)Me(12)(-), characterized by CP-MAS NMR and EXAFS. The cations interact with methyl groups of CB(11)Me(12)(-) with coordination strength increasing from Pb to Ge. Density functional theory (DFT) calculations for the isolated ion pairs, Me(3)M(+)CB(11)Me(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 S(E)2 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(11)H(12)(-) and CB(11)Me(12)(-) 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 CB(11)Me(12)(-), roughly half is on the cage carbon and the rest on methyls 7-12.

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Citations

Aug 16, 2013·Chemical Reviews·Christos Douvris, Josef Michl
Apr 20, 2012·Inorganic Chemistry·Abdul WahabJosef Michl
Jul 13, 2005·Chemical Communications : Chem Comm·Eduardo MolinosAndrew S Weller
Oct 22, 2016·Chemistry : a European Journal·Philipp BertoccoKathrin Stirnat
Feb 17, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Yunjun ShenSimon Duttwyler
Feb 25, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Russell N Grimes
Apr 13, 2018·Angewandte Chemie·Marian OlaruJens Beckmann
Dec 12, 2012·European Journal of Mass Spectrometry·Paola AntoniottiFelice Grandinetti
Sep 16, 2011·Chemistry : a European Journal·Annemarie SchäferThomas Müller
Dec 13, 2012·Chemistry : a European Journal·René T BoeréTracey L Roemmele
Mar 21, 2020·Chemical Communications : Chem Comm·Maria TalaveraThomas Braun
Dec 18, 2020·Chemistry : a European Journal·Jakob-Jonathan MaudrichLars Wesemann
May 22, 2008·Journal of the American Chemical Society·Jaroslav VacekJosef Michl
Oct 8, 2009·The Journal of Physical Chemistry. a·Lauri LippingIlmar A Koppel
Aug 16, 2011·Journal of the American Chemical Society·Annemarie SchäferThomas Müller
Dec 13, 2016·Inorganic Chemistry·Abdul WahabJosef Michl
May 4, 2006·Journal of the American Chemical Society·Ilya ZharovJosef Michl
Oct 9, 2007·Journal of the American Chemical Society·Benjamin T KingJosef Michl
Dec 15, 2006·Chemical Reviews·Stefanie KörbeJosef Michl
Jul 21, 2005·Journal of the American Chemical Society·Francesc TeixidorClara Viñas

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