A Stable but Highly Reactive Phosphine‐Coordinated Borenium: Metal‐free Dihydrogen Activation and Alkyne 1, 2‐Carboboration1. Issue 19 (20th March 2015)

• Record Type: Journal Article
• Authors: Devillard, Marc; Brousses, Rémy; Miqueu, Karinne; Bouhadir, Ghenwa; Bourissou, Didier
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 19(2015)
• Page Start: 5722
• Page End: 5726
• Publication Date: 2015-03-20
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201500959
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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 P<italic>t</italic>Bu₃ (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 P<italic>t</italic>Bu₃ 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.</p> </abstract>