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Hydrogenation of Multiple Bonds by Geminal Aminoborane‐Based Frustrated Lewis Pairs
Author(s) -
Yepes Diana,
Jaque Pablo,
Fernández Israel
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201800864
Subject(s) - geminal , frustrated lewis pair , chemistry , nucleophile , reactivity (psychology) , density functional theory , computational chemistry , boron , boranes , hydrogen bond , hydrogen atom , hydride , atom (system on chip) , medicinal chemistry , lewis acids and bases , stereochemistry , hydrogen , photochemistry , molecule , organic chemistry , catalysis , group (periodic table) , medicine , alternative medicine , pathology , computer science , embedded system
The hydrogenation reaction of multiple bonds that is mediated by geminal aminoborane‐based frustrated Lewis pairs (FLPs) has been explored by means of density functional theory calculations. It was found that the release of the activated dihydrogen occurred in a concerted, yet highly asynchronous, manner. The physical factors that control the transformation were quantitatively described in detail by using the activation strain model of reactivity in combination with the energy decomposition analysis method. This approach suggested a cooperative double hydrogen‐transfer mechanism, which involves the initial migration of the protic (N)H followed by the nucleophilic attack of the (B)H hydride to the carbon atom of the multiple bond. The influence of both the substituents directly attached to the boron atom of the initial FLP and the nature of the multiple bond on the transformation was also investigated.