Kyne, S. H., Schiesser, C. H. and Matsubara, H. (2011) An ab initio and DFT study of radical addition reactions of imidoyl and thioyl radicals to methanimine. Organic and Biomolecular Chemistry, 9 (9). pp. 3217-3224. ISSN 1477-0520
Full content URL: http://dx.doi.org/10.1039/c1ob05105a
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Org. Biomol. Chem. 2011 Kyne.pdf - Whole Document Restricted to Repository staff only 800kB |
Item Type: | Article |
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Item Status: | Live Archive |
Abstract
Ab initio and DFT calculations reveal that both imidoyl and thioyl radicals add to the nitrogen end of methanimine through simultaneous SOMO-pi*imine, SOMO-piimine, SOMO-LPN and pi*radical-LPN interactions between the radical and the imine. At the CCSD(T)/cc-pVDZ//BHandHLYP/cc-pVTZ level of theory, barriers of 13.8 and 26.1 kJ mol-1 are calculated for the attack of the methylimidoyl radical at the carbon- and nitrogen- end of methanimine, respectively, indicating that the imidoyl radial has a preference for addition to the nitrogen end of imine. On the other hand, barriers of 25.1 and 13.4 kJ mol-1 are calculated at the same level of theory for the addition reaction of the methanethioyl radical at the carbon- and nitrogen- end of methanimine, respectively. Natural bond orbital (NBO) analysis at the BHandHLYP/6-311G** level of theory reveals that SOMO-pi*imine, SOMO-piimine, SOMO-LPN and pi*radical-LPN interactions are worth 111, 89, 115 and 17 kJ mol-1, respectively, in the transition state (4) for the reaction of methylimidoyl radical at the nitrogen end of methanimine; similar interactions are observed for the chemistry involving all the radicals studied here. These multi-component interactions are responsible for the unusual motion vectors associated with the transition states involved in these reactions.
Additional Information: | This article is part of themed collection: Free Radical Chemistry special themed issue in memory of Athel Beckwith |
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Keywords: | Ab initio structural calculations, Density functional theory, Intermolecular radical addition |
Subjects: | F Physical Sciences > F160 Organic Chemistry F Physical Sciences > F190 Chemistry not elsewhere classified |
Divisions: | College of Science > School of Chemistry |
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ID Code: | 17618 |
Deposited On: | 11 Jun 2015 11:13 |
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