2006
DOI: 10.1021/jo061275l
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On Gas Phase α-Effects. 1. The Gas-Phase Manifestation and Potential SET Character

Abstract: The possibility of a gas-phase alpha-effect has been explored for the methyl transfer from methyl formate to hydroxide, hydroperoxide, and ethoxide by computing barrier heights at the HF/6-311++G(2df,2p) level of theory. The alpha-nucleophile (hydroperoxide) is found to have a lower barrier than the gas-phase-acidity-matched normal nucleophile (ethoxide) by 3.6 kcal/mol, offering evidence for a gas phase alpha-effect. A Shi-Boyd analysis for these reactions indicates that there is more single-electron-transfer… Show more

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Cited by 47 publications
(64 citation statements)
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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Thus, the enhanced reactivity shown by these nucleophiles was termed the α-effect. 1 Numerous studies have been performed to investigate the cause of the α-effect.…”
Section: Introductionmentioning
confidence: 99%
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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Thus, the enhanced reactivity shown by these nucleophiles was termed the α-effect. 1 Numerous studies have been performed to investigate the cause of the α-effect.…”
Section: Introductionmentioning
confidence: 99%
“…[2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Many theories have been advanced to explain the α-effect, e.g., destabilization of the ground state (GS) due to electronic repulsion between the nonbonding electron pairs, transition state (TS) stabilization including general acid/base catalysis, thermodynamic stability of products, solvent effects. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] However, none of these theories is conclusive. Particularly, solvent effect on the α-effect remains controversial.…”
Section: Introductionmentioning
confidence: 99%
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