Weigand Jan J, Riegel Susanne D, Burford Neil, Decken Andreas
Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4J3, Canada.
J Am Chem Soc. 2007 Jun 27;129(25):7969-76. doi: 10.1021/ja071306+. Epub 2007 Jun 5.
Versatile alkylation reactions give access to symmetric, homoleptic nonsymmetric, and heteroleptic symmetric hexaalkylated 1,2-diphosphonium derivatives as bottleable salts in high yields. A series of 1,2-diphosphonium salts has been isolated and characterized, representing prototypical phosphorus analogues of ethane. Additionally, the solid-state structures for four derivatives have been determined crystallographically. Nonsymmetrically substituted derivatives of 1,2-diphosphonium cations enable the direct observation of 1J(PAPB) coupling constants for two tetracoordinate phosphorus centers. The synthetic approaches promise access to a vast array of derivatives and will provide means to the systematic development of phosphorus analogues of hydrocarbon chemistry.
通用的烷基化反应能够以高产率得到对称、同配非对称和杂配对称的六烷基化1,2 - 二鏻衍生物，作为可瓶装的盐。一系列1,2 - 二鏻盐已被分离和表征，它们是乙烷的典型磷类似物。此外，还通过晶体学确定了四种衍生物的固态结构。1,2 - 二鏻阳离子的非对称取代衍生物能够直接观察到两个四配位磷中心的1J(PAPB)耦合常数。这些合成方法有望获得大量衍生物，并将为系统开发碳氢化合物化学的磷类似物提供手段。
