A Stable but Highly Reactive Phosphine‐Coordinated Borenium: Metal‐free Dihydrogen Activation and Alkyne 1,2‐Carboboration |
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| Authors: | Dr Marc Devillard Dr Rémy Brousses Dr Karinne Miqueu Dr Ghenwa Bouhadir Dr Didier Bourissou |
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| Institution: | 1. Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier/CNRS UMR 5069, 118 Route de Narbonne, 31062 Toulouse Cedex 09 (France) http://lhfa.cnrs.fr/index.php/equipes/lbpb;2. Institut de Chimie de Toulouse (FR 2599), 118 Route de Narbonne, 31062 Toulouse Cedex 09 (France);3. Institut des Sciences Analytiques et de Physico‐Chimie pour l'Environnement et les Matériaux/CNRS UMR 5254, Equipe Chimie Physique, Université de Pau et des Pays de l'Adour, Hélioparc, 2 Avenue du Président Angot, 64053 Pau cedex 09 (France) |
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| Abstract: | Borenium cations have been found to be valuable analogues of boranes as a result of their cationic character which imparts high electrophilicity. Herein, we report the synthesis, characterization, and reactivity of a new type of borenium cation employing a naphthyl bridge and a strong intramolecular P→B interaction. The cation reacts with H2 in the presence of PtBu3 (frustrated Lewis pair (FLP) approach) but also on its own. The mechanism of the reaction between the borenium cation and H2 in the absence of PtBu3 has been investigated using deuterium‐labeling experiments and DFT calculations. Both experiments and calculations imply the side‐on coordination of H2 to the B center, followed by heterolytic splitting and B? C bond cleavage. An uncommon syn 1,2‐carboboration has also been observed upon reaction of the borenium ion with 3‐hexyne. |
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| Keywords: | borenium cations density functional calculations frustrated Lewis pairs H2 activation phosphorus |
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