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首页> 外文学位 >En route to new inorganic rings and polymers: The reactions of chlorine R phosphorus=nitrogen silicon trimethyl (R = chlorine or phenyl) with main group and transition metal chlorides
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En route to new inorganic rings and polymers: The reactions of chlorine R phosphorus=nitrogen silicon trimethyl (R = chlorine or phenyl) with main group and transition metal chlorides

机译：通往新的无机环和聚合物的过程：氯R磷=氮三甲基氮硅（R =氯或苯基）与主要基团和过渡金属氯化物的反应

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摘要

The phosphoranimine Cl$sb3$P = NSiMe$sb3$ has been prepared from the reaction of PCl$sb5$ and Li(N(SiMe$sb3)sb2rbrack $ with a significant improvement in the yield (60%) over literature preparations. The related and previously unknown phosphoranimine, Cl$sb2$PhP = NSiMe$sb3$ was prepared similarily. Reactions of these phosphoranimines with various main group chlorides (PCl$sb5$, PCl$sb3$, SO$sb2rm{Cl}sb2$) afforded the well characterized products ($rm{Clsb3 P(NPClsb2)sb{n} NPClsb3rbrack lbrack PClsb6rbrack }$ (n = 0, 1, 2), Cl$sb3$P = N-PCl$sb2$, and Cl$sb3$P = NSO$sb2$Cl via the facile elimination of ClSiMe$sb3$. Similar reactions with transition metal chlorides (WCl$sb6$, TiCl$sb4$, CpTiCl$sb3$, TaCl$sb5$) were then studied. These reactions yielded the products Cl$sb3$P = N-WCl$sb5$ (1), (Cl$sb3$P = N)$sb2rm{WCl}sb4$ (2), and (Cl$sb2$PhP = N)$sb2rm{WCl}sb4$ (3), respectively. In the cases of the reactions with titanium and tantalum chlorides the products were not fully characterized.;Single crystal X-ray crystallographic studies were performed on 1 and 3. Crystals of 1 are orthorhombic, space group Pcmn, with a = 8.867(4) A, b = 10.749(2) A, c = 12.180(4) A, $alpha = beta = gamma$ = 90$spcirc$, V = 1160.9(7)A$sp3$, and Z = 4. Crystals of 3 are triclinic, space group PI with a = 9.461(4)A, b = 10.099(3)A, c = 14.506(3)A, $alpha$ = 109.65(2)$spcirc$, $beta$ = 97.88(2)$spcirc$, $gamma$ = 94.86(3)$spcirc$, V = 1280.2(7)A$sp3$, and Z = 2.;The phosphoranimine Cl$sb3$P = NSiMe$sb3$ was found to act as a monomer for a room temperature synthesis of high molecular weight linear poly(dichlorophosphazene), (N = P(Cl)$sb2rbracksb{rm n}$. In a similar fashion Cl$sb2$PhP = NSiMe$sb3$ yielded poly(phenylchlorophosphazene), (N = P(Ph)(Cl)) $sb{rm n}$ which had not previously been prepared. Both of these polymers were derivatized via a macromolecular substitution procedure with sodium trifluoroethoxide which afforded the air stable high molecular weight polymers, (N = P(OCH$sb2rm{CF}sb3)sb2rbrack sb{rm n}$ and (N = P(Ph)(OCH$sb2rm{CF}sb3)rbrack sb{rm n}$ which were then fully characterized.
机译：磷酸亚胺Cl $ sb3 $ P = NSiMe $ sb3 $是通过PCl $ sb5 $和Li（N（SiMe $ sb3）sb2rbrack $）的反应制备的，与文献制备相比，收率有显着提高（60％）。类似地制备了相关的和以前未知的磷胺，Cl $ sb2 $ PhP = NSiMe $ sb3 $，得到了这些磷胺与各种主族氯化物（PCl $ sb5 $，PCl $ sb3 $，SO $ sb2rm {Cl} sb2 $）的反应。表征良好的产品（$ rm {Clsb3 P（NPClsb2）sb {n} NPClsb3rbrack lbrack PClsb6rbrack} $（n = 0、1、2），Cl $ sb3 $ P = N-PCl $ sb2 $和Cl $ sb3 $ P = NSO $ sb2 $ Cl，通过轻松消除ClSiMe $ sb3 $。然后研究了与过渡金属氯化物（WCl $ sb6 $，TiCl $ sb4 $，CpTiCl $ sb3 $，TaCl $ sb5 $）的类似反应。得出乘积Cl $ sb3 $ P = N-WCl $ sb5 $（1），（Cl $ sb3 $ P = N）$ sb2rm {WCl} sb4 $（2）和（Cl $ sb2 $ PhP = N）$分别为sb2rm {WCl} sb4 $（3）。在与钛和氯化钽发生反应的情况下，无法充分表征产物。 ；对1和3进行了单晶X射线晶体学研究。1的晶体是正交晶体，空间群Pcmn，a = 8.867（4）A，b = 10.749（2）A，c = 12.180（4）A， $ alpha = beta =γ$ = 90 $ spcirc $，V = 1160.9（7）A $ sp3 $和Z =4。3的晶体是三斜晶的，空间群PI的a = 9.461（4）A，b = 10.099 （3）A，c = 14.506（3）A，$ alpha $ = 109.65（2）$ spcirc $，$ beta $ = 97.88（2）$ spcirc $，$ gamma $ = 94.86（3）$ spcirc $，V ＝ 1280.2（7）A $ sp3 $，且Z ＝ 2；发现磷苯胺亚胺Cl $ sb3 $ P ＝ NSiMe $ sb3 $充当室温合成高分子量线性聚（二氯磷腈）的单体， （N = P（Cl）$ sb2rbracksb {rm n} $。以类似的方式，Cl + sb 2 $ PhP = NSiMe $ sb 3 $产生了聚（苯基氯磷腈），（N = P（Ph）（Cl））$ sb {rm n} $以前没有制备。这两种聚合物均通过大分子取代程序用三氟乙醇钠衍生化，从而提供了空气稳定的高分子量聚合物，（N = P（OCH $ sb2rm {CF} sb3）sb2rbrack sb {rm n} $和（N = P（ Ph）（OCH $ sb2rm {CF} sb3）rbrack sb {rm n} $，然后进行了充分表征。

著录项

  • 作者

    Honeyman, Charles H.;

  • 作者单位

    University of Toronto (Canada).;

  • 授予单位 University of Toronto (Canada).;
  • 学科 Inorganic chemistry.
  • 学位 M.Sc.
  • 年度 1992
  • 页码 145 p.
  • 总页数 145
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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