Institut für Chemie, Universität Rostock, Albert-Einstein-Strasse 3a, 18059 Rostock (Germany) http://www.schulz.chemie.uni-rostock.de/
Angew Chem Int Ed Engl. 2015 Feb 23;54(9):2776-9. doi: 10.1002/anie.201410276. Epub 2015 Jan 21.
Diphosphadiazanediyl, [(μ-NR)P]2 (R=Ter=2,6-dimesitylphenyl), is known to readily activate small molecules with multiple bonds. CO is an especially intriguing species for activation, because either 1,1- or 1,2-bridging mode would lead to a [1.1.1]bicycle or a carbene, respectively. The activation of CO with diphosphadiazanediyl already occurs at ambient temperatures (1 bar, 25 °C). However, CO is involved in an unprecedented ring expansion reaction under preservation of the biradical character, which leads to the formation of the first stable cyclopentane-1,3-diyl analogue displaying photochromic molecular switch characteristics.
二磷杂二氮烯 [(μ-NR)P]2(R=Ter=2,6-二异丙基苯基),已知能轻易激活具有多个键的小分子。一氧化碳是一种特别有趣的活化物种,因为无论是 1,1- 还是 1,2-桥接模式都会分别导致[1.1.1] 自行车或卡宾。二磷杂二氮烯已经在环境温度(1 巴,25°C)下实现了对一氧化碳的活化。然而,一氧化碳在保持双自由基特性的情况下参与了一个前所未有的环扩张反应,生成了第一个稳定的环戊烷-1,3-二基类似物,显示出光致变色分子开关的特性。