Redox-Triggered Reversible Interconversion of a Monocyclic and a Bicyclic Phosphorus Heterocycle
Redox-Triggered Reversible Interconversion of a Monocyclic and a Bicyclic Phosphorus Heterocycle
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DOI：
10.1002/anie.201402884
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发表时间：
2014-06-01
影响因子：
16.6
通讯作者：
Gruetzmacher, Hansjoerg
中科院分区：
文献类型：
--
作者：
Heift, Dominikus;Benko, Zoltan;Gruetzmacher, Hansjoerg
在氧化或还原过程中显着且可逆地改变其结构的分子有潜力成为智能材料的未来组成部分。这种应用的先决条件是分子应在合理的电化学窗口内经历氧化还原耦合转变并锁定稳定的氧化还原态。磷酸乙炔钠与两当量的二环己基碳二亚胺 (DCC) 反应，生成阴离子亚氨基官能化 1,3,5-二氮杂膦烷 [3a](-)。该阴离子被元素碘氧化会引起分子内重排反应，生成双环 1,3,2-二氮杂磷鎓阳离子 [6](+)。这种电子性质从非芳香族到高度芳香族的翻转是可逆的，并且阳离子 [6](+) 用元素镁还原以重新形成 1,3,5-二氮杂膦阴离子 [3a](-)。理论计算表明，膦亚基物种参与了重排过程。
Molecules which change their structures significantly and reversibly upon an oxidation or reduction process have potential as future components of smart materials. A prerequisite for such an application is that the molecules should undergo the redox-coupled transformation within a reasonable electrochemical window and lock into stable redox states. Sodium phosphaethynolate reacts with two equivalents of dicyclohexylcarbodiimide (DCC) to yield an anionic, imino-functionalized 1,3,5-diazaphosphinane [3a](-). The oxidation of this anion with elemental iodine causes an intramolecular rearrangement reaction to give a bicyclic 1,3,2-diazaphospholenium cation [6](+). This umpolung of electronic properties from non-aromatic to highly aromatic is reversible, and the cation [6](+) is reduced with elemental magnesium to reform the 1,3,5-diazaphosphinanide anion [3a](-). Theoretical calculations suggest that phosphinidene species are involved in the rearrangement processes.