- Gas-Phase Hydrogen-Deuterium Exchange Reactions of Anions: Kinetics and Detailed Mechanism
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Rate coefficients and branching ratios for anionic hydrogen-deuterium exchange reactions between isotopically labeled hydroxide, amide, hydrogen sulfide, and methoxide ions and their corresponding neutral compounds have been measured in the gas phase by using the selected ion flow tube (SIFT) technique.The kinetic data for the methoxide-methanol systems lead to a determination of the relative base strength of CD3O(1-) and CH3O(1-).The reaction efficiencies and branching ratios of hydroxide-water, amide-ammonia, and amide-water systems are discussed in terms of the mechanism by which exchange occours; the multiply labeled systems reveal that more proton transfer occur than one might expect upon initial inspection of the data.The product distributions are discussed in terms of relative ion-molecule complex lifetimes and dissociation of the complex is competition with scrambling.Efficient H/D exchange was also observed to occur between compounds containing second-row elements and the implications of this are discussed.
- Grabowski, Joseph J.,DePuy, Charles H.,Doren, Jane M.Van,Bierbaum, Veronica, M.
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- On the Mechanism of Base-Induced Gas-Phase Elimination Reactions of Ethers
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For the base-induced gas-phase elimination reactions of diethyl ether and cis- and trans-1-tert-butyl-4-methoxy-cyclohexane the kinetic isotope and leaving group effects have been determined as functions of the base strength using the method of Fourier transform ion cyclotron resonance mass spectrometry.The results are interpreted in terms of a variable E2 transition-state structure.Increasing the base strength causes the transition state to shift toward the carbanion or E1cb region of the E2 spectrum, which is also a general phenomenon in the condensed phase.Moreover, it appears that the elimination reactions most readily proceed via a transition state in which the β hydrogen and leaving group are periplanar.If the substrate does not easily allow such a relationship, the transition state is found to shift toward the carbenium ion or E1 region of the E2 spectrum where the geometric restrictions of the substrate are less perceptible.The concept of syn/anti dichotomy is used to explain the formation of tree and solvated alkoxide anions in the reactions induced by OH-.Anti elimination is believed to result in the formation of free alkoxide.Syn elimination, which takes advantage of the electrostatic interaction between the base and leaving group, is held responsible for the formation of solvated alkoxide.The importance of base/leaving group association in the transition state of the syn elimination is demonstrated by the low yield of solvated alkoxide in the reaction of OH-, solvated by a dimethylamine molecule, with diethyl ether.Finally, it seems that the selectivity of gas-phase elimination reactions is determined by not only the relative heights of the intrinsic reaction barriers, but also the relative stabilities of the ion/molecule complexes preceding the reaction barriers.
- Koning, Leo J. de,Nibbering, Nico M. M.
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p. 1715 - 1722
(2007/10/02)
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