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  Computational Replication of the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Solution Hydride Transfer Reactions: Supporting the Isotopically Different Tunneling Ready State Conformations

Derakhshani-Molayousefi, M., Kashefolgheta, S., Eilers, J. E., & Lu, Y. (2016). Computational Replication of the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Solution Hydride Transfer Reactions: Supporting the Isotopically Different Tunneling Ready State Conformations. The Journal of Physical Chemistry A, 120(25), 4277-4284. doi:10.1021/acs.jpca.6b03571.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-002A-D9DF-6 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002D-BDFD-C
Genre: Journal Article

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 Creators:
Derakhshani-Molayousefi, Mortaza, Author
Kashefolgheta, Sadra1, Author              
Eilers, James E., Author
Lu, Yun, Author
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1Ana Vila Verde, Theorie & Bio-Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society, ou_2205638              

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 Abstract: We recently reported a study of the steric effect on the 1° isotope dependence of 2° KIEs for several hydride transfer reactions in solution (J. Am. Chem. Soc. 2015, 137, 6653). The unusual 2° KIEs decrease as the 1° isotope changes from H to D, and more in the sterically hindered systems. These were explained in terms of a more crowded tunneling ready state (TRS) conformation in D-tunneling, which has a shorter donor-acceptor distance (DAD), than in H-tunneling. In order to examine the isotopic DAD difference explanation, in this paper, following an activated motion-assisted H-tunneling model that requires a shorter DAD in a heavier isotope transfer process, we computed the 2° KIEs at various H/D positions at different DADs (2.9 Å to 3.5 Å) for the hydride transfer reactions from 2-propanol to the xanthylium and thioxanthylium ions (Xn+ and TXn+) and their 9-phenyl substituted derivatives (Ph(T)Xn+). The calculated 2° KIEs match the experiments and the calculated DAD effect on the 2° KIEs fits the observed 1° isotope effect on the 2° KIEs. These support the motion-assisted H-tunneling model and the isotopically different TRS conformations. Furthermore, it was found that the TRS of the sterically hindered Ph(T)Xn+ system does not possess a longer DAD than that of the (T)Xn+ system. This predicts a no larger 1° KIE in the former system than in the latter. The observed 1° KIE order is, however, contrary to the prediction. This implicates the stronger DAD-compression vibrations coupled to the bulky Ph(T)Xn+ reaction coordinate.

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 Dates: 2016-05-272016-06-30
 Publication Status: Published in print
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 Identifiers: DOI: 10.1021/acs.jpca.6b03571
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Title: The Journal of Physical Chemistry A
Source Genre: Journal
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Publ. Info: American Chemical Society
Pages: - Volume / Issue: 120 (25) Sequence Number: - Start / End Page: 4277 - 4284 Identifier: ISSN: 1089-5639