Kinetics of the Addition of Olefins to Si-Centered Radicals: The Critical Role of Dispersion Interactions Revealed by Theory and Experiment

Abstract

Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions?Contact the NRC Publications Archive team at PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://doi.org/10.1021/acs.jpca.5b03251Access and use of this website and the material on it are subject to the Terms and Conditions set forth at Kinetics of the addition of olefins to Si-centered radicals: The critical role of dispersion interactions revealed by theory and experiment Johnson, Erin R.; Clarkin, Owen J.; Dale, Stephen G.; Dilabio, Gino A.http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/droits L'accès à ce site Web et l'utilisation de son contenu sont assujettis aux conditions présentées dans le site

Thirty Years of (TMS)3SiH: A Milestone in Radical-Based Synthetic Chemistry

“…Quantum mechanical calculations indicated that the reactivity of (TMS) 3 Si • radical toward terminal olefins is due to antagonist polar and enthalpy effects . By comparing theoretical and experimental results for rate constants of a set of olefin addition reactions, it was found that dispersion interactions play a key role in the thermodynamics and kinetics of addition reactions, particularly for sterically bulky radicals like (TMS) 3 Si • or surfaces …”

“…141 By comparing theoretical and experimental results for rate constants of a set of olefin addition reactions, it was found that dispersion interactions play a key role in the thermodynamics and kinetics of addition reactions, particularly for sterically bulky radicals like (TMS) 3 Si • or surfaces. 142 Few examples of early work on hydrosilylation process (173 → 174) under standard experimental conditions (toluene, AIBN, 80 °C) are shown in Scheme 52. 140 Analogous reactions were performed using tetrahydropyran or cyclopentyl methyl ether as the solvent and 2,2′-azobis(dimethylvaleronitrile) as the initiator at 70 °C.…”

The Importance of Being Inconsistent

“…Other authors have suggested constraining the potentials of DFT calculations with the correct asymptotic forms [GL12], which is another approach ripe for energy-error analysis. Other alternatives include using Koopman's condition [DFPP13], or the use of a model for the exchange hole that avoids the delocalization effect on barrier heights [JCDD15]. The beauty of HF-DFT is that it bypasses the need to find a better potential or do a more expensive calculation.…”

Are Dispersion Corrections Accurate Outside Equilibrium? A Case Study on Benzene

“…The past decade has seen an increasing awareness of the role played by van der Waals dispersion forces in chemistry and materials science [1][2][3][4][5][6] . It has consequently become firmly established that including dispersion forces can be vital for understanding and predicting the behaviour and structure of molecules, materials and surfaces [7][8][9][10][11][12] .…”