Solvent Effect on Reaction Barriers. The SN2 Reaction. 1. Application to the Identity Exchange

Sason S. Shaik

doi:10.1021/ja00317a010

Solvent Effect on Reaction Barriers. The S_N2 Reaction. 1. Application to the Identity Exchange

Sason S. Shaik^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

66 Scopus citations

Abstract

The valence-bond (VB) state correlation diagram model¹ is utilized to derive reactivity factors for S_N2 nucleophiles (N^-) and substrates (RX) in various solvents. These reactivity factors are applied to analyze reactivity patterns in the ensemble of the identity reactions (X^- + CH₃X ➛➛ XCH₃ + X^-) and to bridge between gas-phase reactivity and reactivity in solutions. The trends in the reaction barriers are shown to arise from the interplay of intrinsic reactant properties and solvent properties in a manner which reflects the nature of S_N2 as a transformation involving a single electron shift attended by bond interchange.

Original language	English
Pages (from-to)	1227-1232
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	106
Issue number	5
DOIs	https://doi.org/10.1021/ja00317a010
State	Published - 1 Feb 1984
Externally published	Yes

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abstract = "The valence-bond (VB) state correlation diagram model1 is utilized to derive reactivity factors for SN2 nucleophiles (N-) and substrates (RX) in various solvents. These reactivity factors are applied to analyze reactivity patterns in the ensemble of the identity reactions (X- + CH3X ➛➛ XCH3 + X-) and to bridge between gas-phase reactivity and reactivity in solutions. The trends in the reaction barriers are shown to arise from the interplay of intrinsic reactant properties and solvent properties in a manner which reflects the nature of SN2 as a transformation involving a single electron shift attended by bond interchange.",

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AB - The valence-bond (VB) state correlation diagram model1 is utilized to derive reactivity factors for SN2 nucleophiles (N-) and substrates (RX) in various solvents. These reactivity factors are applied to analyze reactivity patterns in the ensemble of the identity reactions (X- + CH3X ➛➛ XCH3 + X-) and to bridge between gas-phase reactivity and reactivity in solutions. The trends in the reaction barriers are shown to arise from the interplay of intrinsic reactant properties and solvent properties in a manner which reflects the nature of SN2 as a transformation involving a single electron shift attended by bond interchange.

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Solvent Effect on Reaction Barriers. The S_N2 Reaction. 1. Application to the Identity Exchange

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