3 years ago

Dynamical Effects along the Bifurcation Pathway Control Semibullvalene Formation in Deazetization Reactions

Dynamical Effects along the Bifurcation Pathway Control
Semibullvalene Formation in Deazetization Reactions
Nilangshu Mandal, Ayan Datta
Post-transition-state dynamics during the deazetization of 3 resulting in two degenerate semibullvalenes (4 and 5) have been investigated with density functional theory (DFT) and quasi-classical trajectory (QCT) calculations. Removal of N2 from 3 occurs through a synchronous and concerted pathway through an ambimodal transition-state (TS1). In addition to TS2, the exclusively anticipated product from minimum energy pathway (MEP) calculations, trajectories initiated from TS1 produce 4, TS2, and 5 in 1:1:1 ratio. Isotopic substitutions (12C(13C/14C)-H(D) at 1–2 positions) result in purely Newtonian kinetic isotope effects (4:5 ≈ 1.4 for 13C113C2), an unequivocal evidence for dynamics controlled product formation.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcb.7b09533

DOI: 10.1021/acs.jpcb.7b09533

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