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Synthesis and derivative chemistry of 2-phosphabutadienes and the reactivity of a two-coordinate phosphine with organolithium reagents.

机译：2-磷丁二烯的合成和衍生物化学以及二配位膦与有机锂试剂的反应性。

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摘要

Since the first report of an iminophosphine that contained a trivalent, dicoordinate phosphorus atom with a (p-p)pi P=N bond, there have been numerous papers on aminoiminophosphines, N-P=N-. In the past decades, phosphorus compounds containing other low-coordinate multiple bonded elements have received more attention. A wide range of species containing P≡X and P=X bonds is now known.;For many years, the chemistry of PIII species has been limited to the reactivity of the lone pair as a nucleophilic center, e.g., the coordination of transition metal centers by the P lone pair. However, in 1992, the synthesis of a 2-phospha-3-methylbutadiene (1, R = Me) via an "ene" reaction by Angelov and Neilson indicated that the 2-coordinate aminophosphine, (Me3Si)2N-P = NSiMe 3 (III), exhibits nucleophilic character as well. In this project by changing the R group, other 2-phosphabutadienes were synthesized and their derivative chemistry was studied. The compounds underwent a wide variety of reactions without disruption of the butadiene moiety, leading to the formation of novel P-functional derivatives and related compounds.*.;With normal phosphines or phosphoranimines, organolithium compounds are often used as addition or substitution reagents. Either way, the organolithium compound acts as a nucleophilic reagent towards phosphorus. By using different organolithium and quenching reagents to study the reactivity of aminoiminophosphine III, we were able to observe the various electronic and steric effects that influence these reactions.*.;The preparative details of these reactions as well as the structural characterization by multinuclear NMR spectroscopy of several representative products are presented.;*Please refer to dissertation for diagrams.
机译：自从首次报道亚氨基膦含有具有（p-p）pi P = N键的三价双配位磷原子以来，已有许多关于氨基亚氨基膦的论文，N-P = N-。在过去的几十年中，含其他低配位多重键合元素的磷化合物受到了越来越多的关注。现已知道各种各样含有P≡X和P = X键的物质。多年来，PIII物质的化学作用一直局限于孤对作为亲核中心的反应性，例如过渡金属的配位以P孤独对为中心。但是，在1992年，Angelov和Neilson通过“烯”反应合成了2-磷-3-甲基丁二烯（1，R = Me），表明2-配位氨基膦（Me3Si）2N-P = NSiMe 3 （III），也表现出亲核特征。在该项目中，通过改变R基团，合成了其他2-phosphabutadienes，并研究了其衍生化学。这些化合物进行了各种各样的反应，而没有破坏丁二烯部分，导致形成新的P-官能衍生物和相关化合物。*;与普通的膦或磷酰胺相比，有机锂化合物通常用作加成或取代试剂。无论哪种方式，有机锂化合物都可以作为对磷的亲核试剂。通过使用不同的有机锂和淬灭剂研究氨基亚氨基膦III的反应性，我们能够观察到影响这些反应的各种电子和空间效应。*;这些反应的制备细节以及多核NMR光谱的结构表征展示了几种具有代表性的产品。; *请参考论文的图表。

著录项

  • 作者

    Jiang, Xiou-Yan.;

  • 作者单位

    Texas Christian University.;

  • 授予单位 Texas Christian University.;
  • 学科 Inorganic chemistry.
  • 学位 Ph.D.
  • 年度 1999
  • 页码 120 p.
  • 总页数 120
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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