Title

Dynamics of Competitive Reactions: Endothermic Proton Transfer and Exothermic Substitution

Document Type

Article

Publication Title

Journal of the American Chemical Society

Department

Chemistry

ISSN

0002-7863

Volume

126

Issue

8

DOI

10.1021/ja030006z

First Page

2640

Last Page

2646

Publication Date

2-1-2004

Abstract

Dynamics of an endothermic proton-transfer reaction, F- with dimethyl sulfoxide, and an endothermic proton-transfer reaction with a competing exothermic substitution (SN2) channel, F- with borane−methyl sulfide complex, were investigated using a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR) and kinetic modeling. The two proton-transfer reactions have slightly positive and a small negative overall free energy changes, respectively. Energy-dependent rate constants were measured as a function of F- ion translational energy, and the resulting kinetics were modeled with the RRKM (Rice−Ramsperger−Kassel−Marcus) theory. The observed rate constants for the proton-transfer reactions of F- with dimethyl sulfoxide and with borane−methyl sulfide complex are identical, with a value of 0.17 × 10-9 cm3 molecule-1 s-1; for the SN2 reaction, k = 0.90 × 10-9 cm3 molecule-1 s-1 at 350 K. Both proton-transfer reactions have positive entropy changes in the forward direction and show positive energy dependences. The competing SN2 reaction exhibits negative energy dependence and becomes less important at higher energies. The changes of the observed rate constants agree with RRKM theory predictions for a few kcal/mol of additional kinetic energy. The dynamic change of the branching ratio for the competing proton transfer and the substitution reactions results from the competition between the microscopic rate constants associated with each channel.

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