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Chemistry of the inner sulfonium salts of dodecahydrododecaborate (2-) anion.

机译：十二氢十二硼酸酯（2-）阴离子的内部salts盐的化学性质。

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摘要

Some aspects of chemistry of the previously known inner methyl sulfonium salts of closo-[B12H12]2− , [Me2SB12H11]−, 1,7- and 1,12-(Me2S)2B12H10, and 1,2-(Me2S)2B12H10, which was isolated and characterized for the first time, have been studied. Reactions with nucleophiles such as phthalimide and thiolate lead to formation of methyl thioethers [MeSB 12H11]2− and [(MeS)(Me2S)B 12H10]−. Excess nucleophile produces methyl dithioethers [(MeS)2B12H10] 2−. Alternatively, [MeSB12H11] 2− and [(MeS)2B12H10] 2− can be obtained by reduction of the corresponding sulfonium salts by sodium or potassium in liquid ammonia. Various derivatives of these thiols have been synthesized through the alkylation and acylation reactions including (Bn2S)2B12H10, 1,7-( i-Pr2S)2B12H10 and [C 6H5C(O)SB12H11]2−. Methyl thioethers have been alkylated by a variety of alkyl halides and tosylates. By this method such functional groups as phosphonate and gem-bisphosphonate can be coupled to the B12-moiety. Propargylation followed by a reaction with B10H12(CH3CN)2 leads to the ortho-carborane-dodecaborane oligomers containing two or three icosahedral cages linked by S(CH3)-CH2 units.; Similar to meta-carborane, electrophilic substitution in 1,7-(Me2S)2B12H10 occurs at positions 9 and 10. Its chloro-, bromo-, iodo-, arylthio- and phenylselenoderivatives have been prepared as well as the bromo- and iododerivatives of the 1,12-isomer. Contrary to the behavior of ortho-carborane, 1,2-(Me 2S)2B12H10 did not produce a single product upon bromination or iodination. The iododerivatives of 1,7- and 1,12-(Me 2S)2B12H10 enter the palladium-catalyzed boron-carbon cross-coupling reactions with Grignard reagents providing B-alkyl- and arylsubstituted derivatives not easily available by any other methods.; All new compounds have been characterized by multinuclear NMR and either mass-spectrometry or elemental analysis. For some the molecular structures have been obtained by X-ray single-crystal diffraction. Several experimental facts have led to the conclusion that in methyl thioethers and thiols the electron density is donated from the cage to a sulfur atom resulting in a partial double-bond character for a B-S bond. (Abstract shortened by UMI.)
机译： closo -[B 12 H 12 ] 2- ，[Me 2 SB 12 H 11 ] -，1,7-和1,12-（ Me 2 S） 2 B 12 H 10 和1,2-（Me 2 <对首次分离并鉴定的/ sub）S）2B 12 H 10 进行了研究。与亲核试剂（例如邻苯二甲酰亚胺和硫醇盐）的反应导致形成甲基硫醚[MeSB 12 H 11 ] 2-和[（MeS）（Me 2 S）B 12 H 10 ] -。过量的亲核试剂产生甲基二硫醚[（MeS） 2 B 12 H 10 ] 2-。或者，[MeSB 12 H 11 ] 2-和[（MeS） 2 B 12 < / sub> H 10 ] 2-可以通过在液氨中用钠或钾还原相应的salts盐来获得。通过烷基化和酰化反应合成了这些硫醇的各种衍生物，包括（Bn 2 S） 2 B 12 H 10 < / sub>，1,7-（ i -Pr 2 S） 2 B 12 H 10 和[C 6 H 5 C（O）SB 12 H 11 ] 2-。甲基硫醚已被各种烷基卤化物和甲苯磺酸盐烷基化。通过这种方法，可以将诸如膦酸酯和 gem -双膦酸酯的官能团偶联至B 12 部分。炔丙基化后与B 10 H 12 （CH 3 CN） 2 反应导致包含两个或三个通过S（CH 3 ）-CH 2 单元连接的二十面体笼的邻位-碳硼烷-十二烷基硼烷低聚物。类似于 meta -carborane，在1,7-（Me 2 S） 2 B 12 H中进行亲电取代 10 发生在9和10位。其氯，溴，碘，芳硫基和苯基硒代衍生物以及1,12-异构体的溴和碘衍生物均已制备。与 ortho -carborane，1,2-（Me 2 S） 2 B 12 H的行为相反溴化或碘化​​后， 10 没有产生单一产物。 1,7-和1,12-（Me 2 S） 2 B 12 H 10 的碘衍生物与格氏试剂一起进入钯催化的硼碳交叉偶联反应，提供 B -烷基和芳基取代的衍生物，这些是其他方法难以获得的。所有新化合物均已通过多核NMR和质谱或元素分析进行​​了表征。对于某些分子，已经通过X射线单晶衍射获得了分子结构。几个实验事实已经得出结论，在甲基硫醚和硫醇中，电子密度从笼中提供给硫原子，导致B-S键具有部分双键特征。 （摘要由UMI缩短。）

著录项

  • 作者

    Kultyshev, Roman G.;

  • 作者单位

    The Ohio State University.;

  • 授予单位 The Ohio State University.;
  • 学科 Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2001
  • 页码 201 p.
  • 总页数 201
  • 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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