z-logo
Premium
A Stable but Highly Reactive Phosphine‐Coordinated Borenium: Metal‐free Dihydrogen Activation and Alkyne 1,2‐Carboboration
Author(s) -
Devillard Marc,
Brousses Rémy,
Miqueu Karinne,
Bouhadir Ghenwa,
Bourissou Didier
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201500959
Subject(s) - heterolysis , chemistry , electrophile , alkyne , reactivity (psychology) , cationic polymerization , frustrated lewis pair , intramolecular force , boranes , medicinal chemistry , phosphine , stereochemistry , carbene , reactive intermediate , bond cleavage , lewis acids and bases , polymer chemistry , boron , organic chemistry , catalysis , medicine , alternative medicine , pathology
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 H 2 in the presence of P t Bu 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 P t Bu 3 has been investigated using deuterium‐labeling experiments and DFT calculations. Both experiments and calculations imply the side‐on coordination of H 2 to the B center, followed by heterolytic splitting and BC bond cleavage. An uncommon syn 1,2‐carboboration has also been observed upon reaction of the borenium ion with 3‐hexyne.

This content is not available in your region!

Continue researching here.

Having issues? You can contact us here