Journal
ORGANIC & BIOMOLECULAR CHEMISTRY
Volume 9, Issue 9, Pages 3217-3224Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c1ob05105a
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- Australian Research Council
- Victorian Institute for Chemical Science High Performance Computing Facility
- Australian Partnership for Advanced Computing National Facility
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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-pi(imine), 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-pi(imine), 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
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