Unimolecular Rearrangements of Carbanions in the Gas Phase. 2. Cyclopropyl Anions

Phillip K. Chou; Gregg D. Dahlke; Steven R Kass

doi:10.1021/ja00054a045

Unimolecular Rearrangements of Carbanions in the Gas Phase. 2. Cyclopropyl Anions

Phillip K. Chou, Gregg D. Dahlke, Steven R Kass

Chemistry (Twin Cities)

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33 Scopus citations

Abstract

We have examined the gas-phase unimolecular rearrangements of a series of substituted cyclopropyl anions ([formula omitted], and CN; X = Y = CO₂CH₃) with a variable temperature flowing afterglow device. The ring opening barriers range from 19 to ≥36 kcal mol⁻¹ and are well reproduced by ab initio molecular orbital calculations. An analysis of eight monosubstituted cyclopropyl anions reveals that the flexibility (ease of inversion) and thermodynamic stability of these ions account for their tendency to isomerize.

Original language	English (US)
Pages (from-to)	315-324
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	115
Issue number	1
DOIs	https://doi.org/10.1021/ja00054a045
State	Published - Jan 1 1993

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abstract = "We have examined the gas-phase unimolecular rearrangements of a series of substituted cyclopropyl anions ([formula omitted], and CN; X = Y = CO2CH3) with a variable temperature flowing afterglow device. The ring opening barriers range from 19 to ≥36 kcal mol−1 and are well reproduced by ab initio molecular orbital calculations. An analysis of eight monosubstituted cyclopropyl anions reveals that the flexibility (ease of inversion) and thermodynamic stability of these ions account for their tendency to isomerize.",

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AU - Dahlke, Gregg D.

AU - Kass, Steven R

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Y1 - 1993/1/1

N2 - We have examined the gas-phase unimolecular rearrangements of a series of substituted cyclopropyl anions ([formula omitted], and CN; X = Y = CO2CH3) with a variable temperature flowing afterglow device. The ring opening barriers range from 19 to ≥36 kcal mol−1 and are well reproduced by ab initio molecular orbital calculations. An analysis of eight monosubstituted cyclopropyl anions reveals that the flexibility (ease of inversion) and thermodynamic stability of these ions account for their tendency to isomerize.

AB - We have examined the gas-phase unimolecular rearrangements of a series of substituted cyclopropyl anions ([formula omitted], and CN; X = Y = CO2CH3) with a variable temperature flowing afterglow device. The ring opening barriers range from 19 to ≥36 kcal mol−1 and are well reproduced by ab initio molecular orbital calculations. An analysis of eight monosubstituted cyclopropyl anions reveals that the flexibility (ease of inversion) and thermodynamic stability of these ions account for their tendency to isomerize.

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Unimolecular Rearrangements of Carbanions in the Gas Phase. 2. Cyclopropyl Anions

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