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Tipping the balance: theoretical interrogation of divergent extended heterolytic fragmentations.


ABSTRACT: Herein we interrogate a type of heterolytic fragmentation reaction called a 'divergent fragmentation' using density functional theory (DFT), natural bond orbital (NBO) analysis, ab initio molecular dynamics (AIMD), and external electric field (EEF) calculations. We demonstrate that substituents, electrostatic environment and non-statistical dynamic effects all influence product selectivity in reactions that involve divergent fragmentation pathways. Direct dynamics simulations reveal an unexpected post-transition state bifurcation (PTSB), and EEF calculations suggest that some transition states for divergent pathways can, in principle, be selectively stabilized if an electric field of the correct magnitude is oriented appropriately.

SUBMITTER: Laconsay CJ 

PROVIDER: S-EPMC7059201 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

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Tipping the balance: theoretical interrogation of divergent extended heterolytic fragmentations.

Laconsay Croix J CJ   Tsui Ka Yi KY   Tantillo Dean J DJ  

Chemical science 20200109 8


Herein we interrogate a type of heterolytic fragmentation reaction called a 'divergent fragmentation' using density functional theory (DFT), natural bond orbital (NBO) analysis, <i>ab initio</i> molecular dynamics (AIMD), and external electric field (EEF) calculations. We demonstrate that substituents, electrostatic environment and non-statistical dynamic effects all influence product selectivity in reactions that involve divergent fragmentation pathways. Direct dynamics simulations reveal an un  ...[more]

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