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Issue 8, 2020
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Tipping the balance: theoretical interrogation of divergent extended heterolytic fragmentations

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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.

Graphical abstract: Tipping the balance: theoretical interrogation of divergent extended heterolytic fragmentations

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Article information


Submitted
11 Oct 2019
Accepted
08 Jan 2020
First published
09 Jan 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 2231-2242
Article type
Edge Article

Tipping the balance: theoretical interrogation of divergent extended heterolytic fragmentations

C. J. Laconsay, K. Y. Tsui and D. J. Tantillo, Chem. Sci., 2020, 11, 2231
DOI: 10.1039/C9SC05161A

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