UNIMOLECULAR REARRANGEMENTS OF CARBANIONS IN THE GAS-PHASE .2. CYCLOPROPYL ANIONS
UNIMOLECULAR REARRANGEMENTS OF CARBANIONS IN THE GAS-PHASE .2. CYCLOPROPYL ANIONS
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DOI：
10.1021/ja00054a045
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发表时间：
1993-01-13
影响因子：
15
通讯作者：
KASS, SR
中科院分区：
文献类型：
--
作者：
CHOU, PK;DAHLKE, GD;KASS, SR
我们使用变温流动余辉装置研究了一系列取代环丙基阴离子（CHXCH2CY-；X = H，Y = Ph，CHO 和 CN；X = Y = CO2CH3）的气相单分子重排。开环势垒范围从 19 到大于或等于 36 kcal mol-1，并且可以通过从头算分子轨道计算很好地重现。对八种单取代环丙基阴离子的分析表明，这些离子的灵活性（易于反转）和热力学稳定性解释了它们异构化的倾向。
We have examined the gas-phase unimolecular rearrangements of a series of substituted cyclopropyl anions (CHXCH2CY-; X = H, Y = Ph, CHO, and CN; X = Y = CO2CH3) with a variable temperature flowing afterglow device. The ring-opening barriers range from 19 to greater-than-or-equal-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.