Heavy‐Atom Tunneling Calculations in Thirteen Organic Reactions: Tunneling Contributions are Substantial, and Bell's Formula Closely Approximates Multidimensional Tunneling at ≥250 K. (18th September 2017)

• Record Type: Journal Article
• Authors: Doubleday, Charles; Armas, Randy; Walker, Dana; Cosgriff, Christopher V.; Greer, Edyta M.
• Is Part Of: Angewandte Chemie. Volume 129:Number 42(2017)
• Page Start: 13279
• Page End: 13282
• Publication Date: 2017-09-18
• Subjects: Bellsche Formel -- Schweratomtunneln -- Transmissionskoeffizienten -- Wignersche Formel; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201708489
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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 SN 2. When compared at the temperatures that give the same effective rate constant of 3×10 −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.