通过由[P2N2]大环稳定的还原锆和铌配合物实现的磷苯基活化。

Phosphorus phenyl-group activation by reduced zirconium and niobium complexes stabilized by the [P2N2] macrocycle.

作者信息

Fryzuk Michael D, Kozak Christopher M, Mehrkhodavandi Parisa, Morello Lara, Patrick Brian O, Rettig Steven J

机构信息

Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada.

出版信息

J Am Chem Soc. 2002 Jan 30;124(4):516-7. doi: 10.1021/ja012100q.

DOI:10.1021/ja012100q

PMID:11804471

Abstract

Reduction of [P2N2]ZrCl2 (where [P2N2] = PhP(CH2SiMe2NSiMe2CH2)2PPh) with KC8 under argon generates the phosphorus phenyl bridged bimetallic complex where the bridging phenyl groups are formally reduced to bis(allyl) dianions. Similar reduction of [P2N2]NbCl caused the one-electron reduction of the phosphorus phenyl group to generate a cyclohexadienyl moiety via a C-C bond formation between the ipso carbons of the two phenyl groups.

摘要

在氩气氛围下，用KC₈还原[P₂N₂]ZrCl₂（其中[P₂N₂] = PhP(CH₂SiMe₂NSiMe₂CH₂)₂PPh）生成磷苯基桥联双金属配合物，其中桥联苯基基团形式上还原为双（烯丙基）二价阴离子。[P₂N₂]NbCl的类似还原导致磷苯基发生单电子还原，通过两个苯基的本位碳之间形成C-C键生成一个环己二烯基部分。