An ab initio and DFT study of radical addition reactions of imidoyl and thioyl radicals to methanimine

Kyne, S. H. and 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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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
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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