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首页> 外文学位 >The synthesis, structures, reactivity and polymerization behavior of boron- and sulfur-nitrogen-phosphorus heterocycles and highly strained chalcogen- and boron-bridged [1]ferrocenophanes.
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The synthesis, structures, reactivity and polymerization behavior of boron- and sulfur-nitrogen-phosphorus heterocycles and highly strained chalcogen- and boron-bridged [1]ferrocenophanes.

机译：硼，硫，氮，磷，杂环和高应变硫属元素和硼桥联的[1]二茂铁杂环烯的合成，结构，反应性和聚合行为。

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摘要

The investigation of the chemistry of the boratophosphazene N(PCl 2NMe)2BCl2 led to the first examples of borazine-phosphazene hybrid cations [N(PCl2NMe)2BCl]+, which possess planar rings, and are formally hybrids of two textbook classes of inorganic heterocycles. The skeletal replacement of a boron atom in an inorganic ring with a heteroelement has been discovered from the treatment of N(PCl 2NMe)2BCl2 with Ag[AsF6] or Ag[SbF 6]. This provides a novel approach to the synthesis of heterocycles containing As(V) and Sb(V) which are difficult to prepare via conventional routes.; The thionylphosphazene cation [NSO(NPCl2)2] +, was synthesized as a highly reactive intermediate, which cleaves diethyl ether to yield the sulfur-ethoxy substituted species, NSO(OCH 2CH3)(NPCl2)2, and reacts with 1,2-dichloroethane to yield NSO(CH2CHCl2)(NPCl2)2. Treatment of NSOCl(NPCl2)2 with SbCl5 produces macrocycles, [NSOCl(NPCl2)2]n (n = 2--6); whereas the similar reaction with GaCl3 provides a new, convenient, ambient temperature route to poly(thionylphosphazene) [NSOCl(NPCl2) 2]n. These transformations presumably occur via a cationic mechanism.; The reactions of cyclic thionylphosphazenes NSOX(NPCl2) 2 (X = Cl or F) with three oxygen-based nucleophiles [NaOPh, NaOCH 2CF3 and NaOBu] were found to proceed regioselectively; first at phosphorus and secondly at sulfur. The substitution of the rings has been extended to the synthesis of new mixed substituent poly[(alkoxy/amino)thionylphosphazenes] which are useful in pressure sensing composite materials.; The first examples of highly strained sulfur-, selenium- and boron-bridged [1]ferrocenophanes have been synthesized and the ring-tilts (>31°) are the largest for any known [1]ferrocenophane. Extended Huckel MO calculations were performed and predicted a decrease in the HOMO-LUMO gap as the ring tilt increases from ferrocene to Fe(eta-C5H4)2S. Thermal and anionic ROP of Fe(eta-C5H3Me)2S yields the first soluble poly(ferrocenylsulfide).
机译：对硼磷磷腈N（PCl 2NMe）2BCl2的化学研究导致了硼嗪-磷腈杂化阳离子[N（PCl2NMe）2BCl] +的第一个实例，它们具有平面环，是两种教科书类型的无机杂环的杂化体。通过用Ag [AsF6]或Ag [SbF 6]处理N（PCl 2NMe）2 BCl 2已发现无机环中的硼原子被杂原子取代。这为合成含As（V）和Sb（V）的杂环提供了一种新颖的方法，这些化合物很难通过常规途径制备。合成了亚硫酰基磷腈阳离子[NSO（NPCl2）2] +作为高反应性中间体，该中间体裂解二乙醚产生硫-乙氧基取代的物质NSO（OCH 2CH3）（NPCl2）2，并与1,2-反应二氯乙烷制得NSO（CH2CHCl2）（NPCl2）2。用SbCl5处理NSOC1（NPCl2）2产生大环，[NSOC1（NPCl2）2] n（n ＝ 2--6）； n ＝ 2--6。而与GaCl3的类似反应为聚（亚硫酰磷腈）[NSOC1（NPCl2）2] n提供了一种新的，方便的环境温度途径。这些转变大概是通过阳离子机制发生的。发现环状亚硫酰磷腈NSOX（NPCl2）2（X = Cl或F）与三种基于氧的亲核试剂[NaOPh，NaOCH 2CF3和NaOBu]进行区域选择性反应；首先是磷，其次是硫。环的取代已扩展到新的混合取代基聚[（烷氧基/氨基）亚硫酰磷腈]的合成，其可用于压力感测复合材料。已经合成了高张力的硫，硒和硼桥联的[1]二茂铁硼烷的第一个实例，对于任何已知的[1]二茂铁琉烷，环-倾斜角（> 31°）最大。进行了扩展的Huckel MO计算，并预测了当环倾斜度从二茂铁向Fe（eta-C5H4）2S增大时，HOMO-LUMO间隙会减小。 Fe（eta-C5H3Me）2S的热和阴离子ROP产生第一种可溶的聚二茂铁硫化物。

著录项

  • 作者

    Gates, Derek Patrick.;

  • 作者单位

    University of Toronto (Canada).;

  • 授予单位 University of Toronto (Canada).;
  • 学科 Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 1997
  • 页码 221 p.
  • 总页数 221
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 无机化学;
  • 关键词

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