Insertions of Cyclic and Acyclic Germanium and Tin Heterocarbenoids into Phosphorus–Chlorine Bonds: Syntheses, Structures, and Reactivities
作者:Joseph K. West、Lothar Stahl
DOI:10.1021/om3000168
日期:2012.3.12
Chloro(organo)phosphines are important precursors to diphosphenes and cyclic oligophosphines. Although chloro(organo)phosphines are commonly reduced with bulk metals (e.g., Na, Mg, and Zn), these reactions are much more selective when done homogeneously. To test whether group 14 heterocarbenoid reductions yield isolable insertion products, the mono- and dichloro(organo)phosphines PhPCl2 (A), Ph2PCl
氯(有机)膦是二膦和环状低聚膦的重要前体。尽管氯(有机)膦通常会被大块金属(例如Na,Mg和Zn)还原,但这些反应在均相时选择性更高。为了测试第14组异类胡萝卜素的还原是否可产生可分离的插入产物,单和二氯(有机)膦PhPCl 2(A),Ph 2 PCl(B),t BuPCl 2(C),t Bu 2 PCl(D)和双(二氯膦基)甲烷(PCl 2)2 CH 2(E)用环状Me 2 Si(μ- Nt Bu)2 El(El = Ge(1),Sn(2))和非环状[[Me 3 Si)2 N] 2 El(El = Ge(3),Sn(4))杂类化合物。在空间上最少受累的膦的反应性更高,而环状亚环苯乙烯基2的反应性最高,而无环次亚甲基3的反应性最低。除一种产品外,所有产品均为单插入或双插入化合物,唯一的例外是衍生自2的二萘烷。半动力学和结构数据表明,四价的14族化合物是通过一种插入机理形成的,其插入速率取决