Abstract
The reaction mechanism for the hydrogenation of norbornadiene (nbd) catalysed by bis-norbornadiene rhodium(I) [Rh(nbd)2]+ complex has been studied by means of DFT based methods, in the absence and in the presence of a self-folding octaamide cavitand. Formation of three products, norbornene, nortricyclene and a dimer is discussed. When the metal complex is encapsulated inside the cavitand, the steric crowding prevents formation of the dimer, while in the absence of the cavity, the dimer is the major product. Although energy differences between the studied reaction pathways are small, the present study explains the changes in regioselectivity when the hydrogenation reaction is carried out in a confined space.
Keywords: Cavitands, Supramolecular, Catalysis, Rhodium, Hydrogenation, DFT.
Current Organic Chemistry
Title:Mechanisms of Catalysis in Confined Spaces: Hydrogenation of Norbornadiene with a Rhodium Complex included in a Self-Folding Cavitand
Volume: 17 Issue: 14
Author(s): Alex Hamilton, Michael Gicquel, Pablo Ballester and Carles Bo
Affiliation:
Keywords: Cavitands, Supramolecular, Catalysis, Rhodium, Hydrogenation, DFT.
Abstract: The reaction mechanism for the hydrogenation of norbornadiene (nbd) catalysed by bis-norbornadiene rhodium(I) [Rh(nbd)2]+ complex has been studied by means of DFT based methods, in the absence and in the presence of a self-folding octaamide cavitand. Formation of three products, norbornene, nortricyclene and a dimer is discussed. When the metal complex is encapsulated inside the cavitand, the steric crowding prevents formation of the dimer, while in the absence of the cavity, the dimer is the major product. Although energy differences between the studied reaction pathways are small, the present study explains the changes in regioselectivity when the hydrogenation reaction is carried out in a confined space.
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Cite this article as:
Hamilton Alex, Gicquel Michael, Ballester Pablo and Bo Carles, Mechanisms of Catalysis in Confined Spaces: Hydrogenation of Norbornadiene with a Rhodium Complex included in a Self-Folding Cavitand, Current Organic Chemistry 2013; 17 (14) . https://dx.doi.org/10.2174/1385272811317140006
DOI https://dx.doi.org/10.2174/1385272811317140006 |
Print ISSN 1385-2728 |
Publisher Name Bentham Science Publisher |
Online ISSN 1875-5348 |
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