CB11Me11 Boronium Ylides: Carba-closo-dodecaboranes with a Naked Boron Vertex
- 5 April 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 128 (18), 6089-6100
- https://doi.org/10.1021/ja054256m
Abstract
In pentane solution, 2 equiv of the icosahedral CB11Me12• radical cleaves the Si−Si bond of hexaalkyldisilanes by boron to silicon methyl transfer with formation of 2 equiv of methyltrialkylsilanes. The loss of a methyl radical converts the CB11Me12• radical into an internally charge-compensated “boronium ylide” CB11Me11 with a naked vertex, which can be formally viewed as a deprotonated hypercloso carborane. It has been isolated as an air-sensitive solid, stable only below ∼ −60 °C. The naked vertex appears to be in position 12 since the material reacts instantaneously with alcohols and ethers to form the 12-alkoxy anions 12-CB11Me11OR. It reacts with many other nucleophiles to yield more complex mixtures containing similar products. DFT calculations for the four CB11Me11 isomers give closed-shell ground-state electronic structures. For the isomer with naked vertex 12, a DFT computational search failed to reveal any skeletal dimers, apparently due to excessive methyl−methyl repulsions, and only a cyclic dimer bound through weak interactions of one of the 7-methyl hydrogen atoms on each cage with the empty exocyclic orbitals on B12 of the other cage was found. Natural hybrid orbital populations suggest that the three possible isomers of monomeric boronium ylides are close to true singlet ylides, with triplet states ∼50 kcal/mol higher. The calculated electronic structure of the carbonium ylide is close to a singlet carbene, with a triplet state ∼16 kcal/mol higher. An attempted preparation of Me3C+CB11Me12- yielded neopentane and products consistent with a sequential loss of methyl groups from the carborane cage with a transient formation of similar boronium ylides. Probable mechanisms of these methyl transfer reactions are considered, and the possibly quite general role of “ylide” structures in Lewis acid induced substitution reactions on the boron vertices of carboranes and boranes is noted.Keywords
This publication has 57 references indexed in Scilit:
- A New Type of Intermediate, C+(BCH3)11-↔ C(BCH3)11, in a Grob Fragmentation Coupled with Intramolecular Hydride Transfer. A Nonclassical Carbocation Ylide or a Carbenoid?Journal of the American Chemical Society, 2004
- Metal Cation−Methyl Interactions in CB11Me12- Salts of Me3Ge+, Me3Sn+, and Me3Pb+Journal of the American Chemical Society, 2004
- Li+-Induced σ-Bond Metathesis: Aryl for Methyl Exchange on Boron in a Methylated Monocarbadodecaborate AnionJournal of the American Chemical Society, 2004
- Crystal Structure of n-Bu3Sn+ CB11Me12-Journal of the American Chemical Society, 2000
- A novel synthetic route to peralkylated carborane anions, 1-H-CB9Me9− and 1-H-CB11R11− (R = Me, Et)Chemical Communications, 2000
- Dodecamethylcarba-closo-dodecaborate(−) Anion, CB11Me12-Journal of the American Chemical Society, 1996
- New Weakly Coordinating Anions. III. Useful Silver and Trityl Salt Reagents of Carborane AnionsJournal of the American Chemical Society, 1994
- A new carborane-ylide reaction. Synthesis and structural characterization of a seven-vertex nido-carborane zwitterion: exo-6-(Me3P+CH2)-3,4-Et2-nido-3,4-C2B5H5-Organometallics, 1992
- Electrophilic reactions of protonated closo-B10H102- with arenes, alkane carbon-hydrogen bonds, and triflate ion forming aryl, alkyl, and triflate nido-6-X-B10H13 derivativesJournal of the American Chemical Society, 1992
- High oxidation state monopentamethylcyclopentadienyltungsten methyl complexes including the first d0 complex containing a highly distorted methylene ligand, W(.eta.5-C5Me5)(CH3)3(CH2)Journal of the American Chemical Society, 1987