Metal‐Free Dihydrogen Oxidation by a Borenium Cation: A Combined Electrochemical/Frustrated Lewis Pair Approach

Borenium cations have been found to be valuable analogues of boranes as ar esult of their cationic character which imparts high electrophilicity.H erein, we report the synthesis,c haracterization, and reactivity of an ew type of borenium cation employing an aphthyl bridge and as trong intramolecular P!Binteraction. The cation reacts with H 2 in the presence of PtBu 3 (frustrated Lewis pair (FLP) approach) but also on its own.The mechanism of the reaction between the borenium cation and H 2 in the absence of PtBu 3 has been investigated using deuterium-labeling experiments and DFT calculations.Both experiments and calculations imply the sideon coordination of H 2 to the Bcenter,f ollowed by heterolytic splitting and B À Cb ond cleavage.A nu ncommon syn 1,2carboboration has also been observed upon reaction of the borenium ion with 3-hexyne.ThelastdecadehaswitnessedanupsurgeofinterestinLewis acidic boron-containing compounds,whose archetypal derivative is B(C 6 F 5 ) 3 .I na ddition to their role as co-catalysts in transition-metal-catalyzed reactions,b oranes have shown Angewandte Chemie

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A Stable but Highly Reactive Phosphine‐Coordinated Borenium: Metal‐free Dihydrogen Activation and Alkyne 1,2‐Carboboration

Devillard

Brousses

Miqueu

et al. 2015

Angewandte Chemie

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Katalysepreis der BASF: A. E. Ashley / Hellmuth‐Fischer‐Medaille: M. Arenz / Mattauch‐Herzog‐Preis: K. Koszinowski / OMCOS‐Preis: M. S. Sanford

2015

Angewandte Chemie

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Durch N‐heterocyclische Carbene stabilisierte Borylradikale

et al. 2016

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Die Reaktion von 2-(Trimethylsilyl)imidazoliumtriflat 9 mit Diarylborhalogeniden (4-R-C 6 H 4 ) 2 BX (R = H, X = Br;R = CH 3 ,X = Cl;R = CF 3 ,X = Cl) führte zu den NHC-stabilisierten Boreniumkationen 10 a-c.C yclovoltammetrische Untersuchungen offenbarten eine lineare Korrelation zwischen den Hammett-Parametern s p der para-Substituenten und den Halbstufenpotentialen. Die chemische Reduktion mittels Decamethylcobaltocen, [(C 5 Me 5 ) 2 Co],l ieferte die entsprechenden Radikale 11 a-c;ihre Charakterisierung durch EPR-Spektroskopie bestätigte den paramagnetischen Charakter von 11 a-c und ergab große Hyperfeinkopplungskonstanten zu den Bor-Isotopen 11 Bu nd 10 B, während die Delokalisierung des ungepaarten Elektrons in das NHC vernachlässigbar ist. DFT-Berechnungen der Anteile der Spindichteverteilung zwischen dem Carben (NHC) und dem Borylfragment (BR 2 )o ffenbarte für 11 a-c ein Spindichteverhältnis (BR 2 /NHC) von ca. 9:1, wodurch ihr eindeutiger Borylcharakter unterstrichen wird. Die Molekülstruktur der stabilsten Spezies 11 c wurded urchR çntgenstrukturanalyse bestimmt.

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Metal‐Free Dihydrogen Oxidation by a Borenium Cation: A Combined Electrochemical/Frustrated Lewis Pair Approach

Abstract: In order to use H 2 as a clean source of electricity, prohibitively rare and expensive precious metal electrocata-

Cited by 12 publications

References 17 publications

A Stable but Highly Reactive Phosphine‐Coordinated Borenium: Metal‐free Dihydrogen Activation and Alkyne 1,2‐Carboboration

A Stable but Highly Reactive Phosphine‐Coordinated Borenium: Metal‐free Dihydrogen Activation and Alkyne 1,2‐Carboboration

Katalysepreis der BASF: A. E. Ashley / Hellmuth‐Fischer‐Medaille: M. Arenz / Mattauch‐Herzog‐Preis: K. Koszinowski / OMCOS‐Preis: M. S. Sanford

Durch N‐heterocyclische Carbene stabilisierte Borylradikale

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