Evidence for an Intermediate in the Methylation of CB11 H12 - with Methyl Triflate: Comparison of Electrophilic Substitution in Cage Boranes and in Arenes
Status PubMed-not-MEDLINE Jazyk angličtina Země Německo Médium print-electronic
Typ dokumentu časopisecké články
Grantová podpora
Institute of Organic Chemistry and Biochemistry
61388963
Academy of Sciences of the Czech Republic
CHE-0848477
US National Science Foundation
UV-INV-AE11-41612
Universitat de València
PubMed
31986728
DOI
10.1002/cplu.201300219
Knihovny.cz E-zdroje
- Klíčová slova
- alkylation, boranes, carboranes, electrophilic substitution, hydrogen scrambling,
- Publikační typ
- časopisecké články MeSH
The trideuteriomethylation of BH vertices in CB11 H12 - and its derivatives with CD3 OTf (OTf=triflate, trifluoromethanesulfonate) yields a mixture of BCD3 and BCHD2 substitution products, thus demonstrating the intermediacy of a species with a long enough lifetime for hydrogen scrambling between the boron vertex and the methyl substituent. No such scrambling is observed if CD3 OTf is used to methylate toluene. According to density functional theory calculations, the intermediate in BH vertex methylation is a three-center bonded σ adduct of a methyl cation to the BH bond and the proton scrambling occurs via a transition structure containing a distorted square-pyramidal methane attached axially to a "naked" boron vertex. The subsequent proton or deuteron loss is presently not understood in detail. A general comparison of electrophilic substitution on closo-boranes and arenes is provided and similarities as well as differences are discussed. A recalculation of the optimized geometry of the CB11 Me12 . radical produced a second Jahn-Teller distorted minimum and resulted in a somewhat improved agreement between calculated and measured proton hyperfine coupling constants.
Department de Química Física Universitat de València Dr Moliner 50 46100 Burjassot
Department of Chemistry and Biochemistry University of Colorado Boulder CO 80309 0215
Department of Chemistry Middle East Technical University 06800 Ankara
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