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Statements

Subject Item
n2:RIV%2F61388963%3A_____%2F13%3A00397510%21RIV14-AV0-61388963
rdf:type
n11:Vysledek skos:Concept
dcterms:description
The trideuteriomethylation of BH vertices in CB11H12- and its derivatives with CD3OTf (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 CD3OTf is used to methylate toluene. According to density functional theory calculations, the intermediate in BH vertex methylation is a three-center bonded sigma 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 CB11Me12. radical produced a second Jahn-Teller distorted minimum and resulted in a somewhat improved agreement between calculated and measured proton hyperfine coupling constants. The trideuteriomethylation of BH vertices in CB11H12- and its derivatives with CD3OTf (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 CD3OTf is used to methylate toluene. According to density functional theory calculations, the intermediate in BH vertex methylation is a three-center bonded sigma 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 CB11Me12. radical produced a second Jahn-Teller distorted minimum and resulted in a somewhat improved agreement between calculated and measured proton hyperfine coupling constants.
dcterms:title
Evidence for an Intermediate in the Methylation of CB11H12- with Methyl Triflate: Comparison of Electrophilic Substitution in Cage Boranes and in Arenes Evidence for an Intermediate in the Methylation of CB11H12- with Methyl Triflate: Comparison of Electrophilic Substitution in Cage Boranes and in Arenes
skos:prefLabel
Evidence for an Intermediate in the Methylation of CB11H12- with Methyl Triflate: Comparison of Electrophilic Substitution in Cage Boranes and in Arenes Evidence for an Intermediate in the Methylation of CB11H12- with Methyl Triflate: Comparison of Electrophilic Substitution in Cage Boranes and in Arenes
skos:notation
RIV/61388963:_____/13:00397510!RIV14-AV0-61388963
n11:predkladatel
n12:ico%3A61388963
n3:aktivita
n7:I
n3:aktivity
I
n3:cisloPeriodika
9
n3:dodaniDat
n8:2014
n3:domaciTvurceVysledku
Akdag, Akin n4:7553099 Michl, Josef
n3:druhVysledku
n6:J
n3:duvernostUdaju
n5:S
n3:entitaPredkladatele
n10:predkladatel
n3:idSjednocenehoVysledku
73749
n3:idVysledku
RIV/61388963:_____/13:00397510
n3:jazykVysledku
n14:eng
n3:klicovaSlova
alkylation; boranes; carboranes; electrophilic substitution; hydrogen scrambling
n3:klicoveSlovo
n16:hydrogen%20scrambling n16:alkylation n16:electrophilic%20substitution n16:boranes n16:carboranes
n3:kodStatuVydavatele
DE - Spolková republika Německo
n3:kontrolniKodProRIV
[0AD813B8E7E8]
n3:nazevZdroje
ChemPlusChem
n3:obor
n15:CC
n3:pocetDomacichTvurcuVysledku
3
n3:pocetTvurcuVysledku
5
n3:rokUplatneniVysledku
n8:2013
n3:svazekPeriodika
78
n3:tvurceVysledku
Kaleta, Jiří Piqueras, M. C. Akdag, Akin Crespo, R. Michl, Josef
n3:wos
000324043400037
s:issn
2192-6506
s:numberOfPages
10
n18:doi
10.1002/cplu.201300219