title: Carbodications. 4.(1) Hydrogen Isotope Exchange of Crotonyl Cations in Superacid.
abstract: The title ion reacts in 1:1 DF-SbF(5) and exchanges up to five protium atoms with deuterium. The incorporation of label was measured by GC-MS analysis of the methyl crotonate formed by methanol quenching. The isotopomer distribution at about 60% conversion, which shows a minimum for the d(1) and a maximum for the d(4) species, indicates that the intermediate dication with the second charge at C(3) loses a proton faster from C(4) than from C(2). Formation of the pentadeuteriocrotonyl cation indicates that the 1,4-dication (acyl primary alkyl) or the 1,2-dication must intervene in the process. Computer modeling of the kinetics for the multiple exchange process to fit the experimental deuterium distribution allowed determination of the relative rate constants and isotope effects (KIEs) for the formation of the carbocations from alkenoyl cations (beta-secondary KIE) and elimination from carbodications to alkenoyl cations (primary KIE). An exceptionally large beta-secondary KIE of ca. 2.0/hydrogen was found for the formation of the dication. A small primary isotope effect of ca. 1.5 was found for elimination from the dications to the alkenoyl cations. Elimination from the 1,3-acylalkyl dication to form the nonconjugated 3-butenoyl cation is 6-7 times faster than elimination to the conjugated 2-butenoyl cation. The rate ratio for the conversion of 3-butenoyl cation to the 1,4-dication (primary alkyl cation) and 1,3-dication (secondary alkyl cation) is (0.025-0.030):1, whereas the relative rate of the formation of the 1,2-acylalkyl dication (the alternative route of achieving pentadeuteration) is zero.
authors.affiliation: Department of Chemical and Petroleum Engineering, University of Pittsburgh, 1249 Benedum Hall, Pittsburgh, Pennsylvania 15213.
authors.forename: Dan
authors.initials: D
authors.lastname: F&acaron;rca&scedil;iu
authors.forename: Ursula L.
authors.initials: UL
authors.lastname: Bologa