Khan Arif Ali, Junker Philip, Schnakenburg Gregor, Espinosa Ferao Arturo, Streubel Rainer
University School of Basic and Applied Sciences, Guru Gobind Singh Indraprastha University, Dwarka, Sec.16-C, New Delhi - 110078, India.
Institut für Anorganische Chemie, der Rheinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.
Chem Commun (Camb). 2019 Aug 28;55(67):9987-9990. doi: 10.1039/c9cc05328j. Epub 2019 Aug 1.
The transiently generated electrophilic terminal phosphinidene complex [(CO)WPCH(SiMe)] reacted with allyl halides (X = F, Cl, Br) in toluene resulting in the formation of stable C-X insertion products 3a-c and diastereomeric phosphirane complexes 4a,a',b,b' as well as methylenephosphirane complex 5 as observed by P{H} NMR spectroscopy. DFT calculations revealed that a novel rearrangement of transient phosphirane complexes is responsible involving C → P X atom transfer.
瞬态生成的亲电末端磷烯配合物[(CO)WPCH(SiMe)]与烯丙基卤化物(X = F、Cl、Br)在甲苯中反应，通过磷的{1H}核磁共振光谱观察到，生成了稳定的C-X插入产物3a-c、非对映异构的磷杂环丙烷配合物4a、a'、b、b'以及亚甲基磷杂环丙烷配合物5。密度泛函理论计算表明，瞬态磷杂环丙烷配合物发生了一种涉及C→P X原子转移的新型重排反应。
