Nesterov Vitaly, Espinosa Arturo, Schnakenburg Gregor, Streubel Rainer
Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany), Fax: (+49) 228-739616.
Chemistry. 2014 Jun 2;20(23):7010-6. doi: 10.1002/chem.201305061. Epub 2014 Apr 15.
The reaction of Li/Cl P-CPh3 phosphinidenoid tungsten(0) complex 2 with dimethylcyanamide afforded tricyclic phosphirane complex 4, an unprecedented rearrangement of which led to the novel N,P,C cage complex 6. On the basis of DFT calculations, formation and intramolecular [3+2] cycloaddition of the transient nitrilium phosphane ylide complex 3 to a phenyl ring of the triphenylmethyl substituent to give 4 is proposed. Furthermore, theoretical evidence for terminal N-amidinophosphinidene complex 7, formed by [2+1] cycloelimination from 4, is provided, and the role of the electronic structure and non-covalent interactions of intermediate 7 discussed.
锂/氯-三苯基膦亚磷钨(0)配合物2与二甲基氰胺反应生成了三环磷杂环丙烷配合物4，其前所未有的重排导致了新型N、P、C笼状配合物6的形成。基于密度泛函理论计算，提出了瞬态腈鎓膦叶立德配合物3与三苯甲基取代基的苯环进行分子内[3+2]环加成生成4的过程。此外，还提供了由4通过[2+1]环消除形成的末端N-脒基亚磷烯配合物7的理论证据，并讨论了中间体7的电子结构和非共价相互作用的作用。
