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Deuterium and Carbon-13 Scrambling Processes in Isopropyl Cation

Martin Saunders ; Department of Chemistry, Yale University, New Haven CT 06511-8118, USA
Alan P. Hewett ; Department of Chemistry, Yale University, New Haven CT 06511-8118, USA
Olga Kronja ; Department of Chemistry, Yale University, New Haven CT 06511-8118, USA

Puni tekst: engleski, pdf (14 MB) str. 673-678 preuzimanja: 226* citiraj
APA 6th Edition
Saunders, M., Hewett, A.P. i Kronja, O. (1992). Deuterium and Carbon-13 Scrambling Processes in Isopropyl Cation. Croatica Chemica Acta, 65 (3), 673-678. Preuzeto s https://hrcak.srce.hr/137125
MLA 8th Edition
Saunders, Martin, et al. "Deuterium and Carbon-13 Scrambling Processes in Isopropyl Cation." Croatica Chemica Acta, vol. 65, br. 3, 1992, str. 673-678. https://hrcak.srce.hr/137125. Citirano 25.02.2021.
Chicago 17th Edition
Saunders, Martin, Alan P. Hewett i Olga Kronja. "Deuterium and Carbon-13 Scrambling Processes in Isopropyl Cation." Croatica Chemica Acta 65, br. 3 (1992): 673-678. https://hrcak.srce.hr/137125
Harvard
Saunders, M., Hewett, A.P., i Kronja, O. (1992). 'Deuterium and Carbon-13 Scrambling Processes in Isopropyl Cation', Croatica Chemica Acta, 65(3), str. 673-678. Preuzeto s: https://hrcak.srce.hr/137125 (Datum pristupa: 25.02.2021.)
Vancouver
Saunders M, Hewett AP, Kronja O. Deuterium and Carbon-13 Scrambling Processes in Isopropyl Cation. Croatica Chemica Acta [Internet]. 1992 [pristupljeno 25.02.2021.];65(3):673-678. Dostupno na: https://hrcak.srce.hr/137125
IEEE
M. Saunders, A.P. Hewett i O. Kronja, "Deuterium and Carbon-13 Scrambling Processes in Isopropyl Cation", Croatica Chemica Acta, vol.65, br. 3, str. 673-678, 1992. [Online]. Dostupno na: https://hrcak.srce.hr/137125. [Citirano: 25.02.2021.]

Sažetak
The degenerate rearrangement processes in i-propyl cation were studied using the isotopically double-labeled 2-propyl-2-13C1-2-dI cation (A), which was obtained from the corresponding chloride using the molecular beam technique. The first step in the rearrangement is a shift of one of the methyl hydrogens to form n-propyl cation (or a species in its vicinity on the energy surface), followed by rotation of the methylene group. Rotation in one direction (Process I) leads to formation of isopropyl cation with an interchange of the methine proton with a methyl proton while rotation in the other direction (Process II) results in the formation of intermediate protonated cyclopropane. Through corner-to-corner proton shifts, the isotopes are completely scrambled before the reverse process returns the ion to isopropyl. Relative rates of Processes I and II were determined on the basis of the experimentally established composition of the mixture of isotopomers obtained in an early stage of scrambling, using Runge-Kutta integration to simulate the kinetics. It was found that Process I was faster (ki/k\i = 3.4), meaning, according to the proposed mechanism, that hydrogen scrambles a little more rapidly than carbon.

Hrčak ID: 137125

URI
https://hrcak.srce.hr/137125

Posjeta: 348 *