Heavy‐Atom Tunneling Calculations in Thirteen Organic Reactions: Tunneling Contributions are Substantial, and Bell's Formula Closely Approximates Multidimensional Tunneling at ≥250 K

Autor:	Randy Armas, Edyta M. Greer, Christopher V. Cosgriff, Dana Walker, Charles Doubleday
Rok vydání:	2017
Předmět:	Pericyclic reaction Chemistry 010405 organic chemistry General Chemistry General Medicine Condensed Matter::Mesoscopic Systems and Quantum Hall Effect Ring (chemistry) Curvature 010402 general chemistry Radical cyclization 01 natural sciences Catalysis 0104 chemical sciences Reaction rate constant Organic reaction Computational chemistry Quantum mechanics Atom Quantum tunnelling
Zdroj:	Angewandte Chemie. 129:13279-13282
ISSN:	1521-3757 0044-8249
DOI:	10.1002/ange.201708489
Popis:	Multidimensional tunneling calculations are carried out for 13 reactions, to test the scope of heavy-atom tunneling in organic chemistry, and to check the accuracy of one-dimensional tunneling models. The reactions include pericyclic, cycloaromatization, radical cyclization and ring opening, and SN2. When compared at the temperatures that give the same effective rate constant of 3 x 10-5 s-1, tunneling accounts for 25 - 95% of the rate in 8 of the 13 reactions. Values of transmission coefficients predicted by Bell's formula, κBell, agree well with multidimensional tunneling (canonical variational transition state theory with small curvature tunneling), κSCT. Mean unsigned deviations of κBell vs κSCT are 0.08, 0.04, 0.02 at 250, 300 and 400 K. This suggests that κBell is a useful first choice for predicting transmission coefficients in heavy-atom tunnelling.
Databáze:	OpenAIRE
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