...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Insertion reactions of small unsaturated molecules in the N-B bonds of boron guanidinates
【24h】

Insertion reactions of small unsaturated molecules in the N-B bonds of boron guanidinates

机译：小型非饱和分子在硼胍菌键N-B键中的插入反应

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

We report here 1,1- and 1,2-insertion reactions of small unsaturated molecules in the N-B bonds of two boron guanidinates, (Me2N)C((NPr)-Pr-i)(2)BCy2 (1) and {Pr-i(H)N}C((NPr)-Pr-i){N(p-Bu-t-C6H4)}BCy2 (2), and two bis-boron guanidinates(2-), {Pr-i(BCy2)N}C((NPr)-Pr-i){N(p-Bu-t-C6H4)}BCy2 (3) and {Pr-i(C8H14B)N}C((NPr)-Pr-i){N(p-Me-C6H4)}BC8H14 (4), the latter being prepared for the first time by double deprotonation of the corresponding guanidine with the 9-borabicyclo[3.3.1]nonane dimer, (H-BC8H14)(2). Compounds 1-4 easily insert aromatic isonitriles, XylNC (Xyl = 2,6-Me-2-C6H3) and (p-MeO-C6H4)NC, to give the expected diazaboroles 5-12, some of them being structurally characterised by X-ray diffraction. Interestingly, the BC8H14 derivatives 11 and 12 are in a fast temperature-dependent equilibrium with the de-insertion products, whose thermodynamic parameters are reported here. A correlation between these equilibria and the puckered heterocyclic structure found in the solid state for 11, and confirmed by DFT calculations, is also established. Reactions of the aforementioned guanidinates with CO are more sluggish or even precluded, and only one product, {Pr-i(H)N}C{N(p-Bu-t-C6H4)}((NPr)-Pr-i)(CO)BCy2 (13), could be isolated in moderate yields. The 1,2-insertions of benzaldehyde in compounds 1, 2 and 4 are reversible reactions in all cases, and only one of the insertion products, {Pr-i(H)N}C{N(p-Bu-t-C6H4)}((NPr)-Pr-i)(PhHCO)BCy2 (16a), was isolated and diffractrometrically characterised. Likewise, CO2 reversibly inserts into a N-B bond of 2 to give {Pr-i(H)N}C{N(p-Bu-t-C6H4)}((NPr)-Pr-i)(CO2)BCy2 (19) with a conversion of ca. 9%. In all these equilibria, de-insertion is always favoured upon increasing the temperature.
机译：我们在此报告在两个硼胍的Nb键中的小不饱和分子的1,1-1,2-插入反应，（ME2N）C（（NPR）-1-I）（2）Bcy2（1）和{Pr -i（h）n} c（（npr）-pr-i）{n（p-bu-t-c6h4）} bcy2（2），以及两个双硼胍（2-），{pr-i（ bcy2）n} c（（npr）-pr-i）{n（p-bu-t-c6h4）} bcy2（3）和{pr-1（c8h14b）n} c（（npr）-pr-i） {N（P-ME-C6H4）} BC8H14（4），后者首次制于第一次通过用9-硼双环[3.3.1]壬烷二聚体（H-BC8H14）（2 ）。化合物1-4易于插入芳族异腈，XylnC（Xyl = 2,6-Me-2-C6H3）和（P-Meo-C6H4）NC，得到预期的Diazaboroles 5-12，其中一些在结构上以X结构为特征 - 射线衍射。有趣的是，BC8H14衍生物11和12处于与脱模产品的快速温度依赖性平衡，其在此报告其热力学参数。还建立了这些平衡和褶皱杂环结构的相关性11，并通过DFT计算证实的褶皱杂环结构。上述胍与CO的反应更加缓慢或甚至排除，并且只有一个产品，{PR-I（H）N} C {N（P-BU-T-C6H4）}（（NPR）-PR-I） （CO）BCY2（13），可以以适度的产率分离。在化合物1,2和4中的苯甲醛的1,2-插入是所有情况下的可逆反应，并且只有一个插入产物，{Pr-1（H）N} C {N（P-BU-T-C6H4 （（NPR）-P-I）（PHHCO）BCY2（16A）被分离和衍射表征。同样，CO2可逆地插入2的Nb键2中，得到{Pr-1（H）N} C {N（P-BU-T-C6H4）}（（NPR）-PR-I）（CO2）BCY2（19 ）随着CA的转换。 9％。在所有这些均衡中，在增加温度时，始终有利于脱模。

著录项

  • 来源
  • 作者

    Ramos Alberto; Antinolo Antonio; Carrillo-Hermosilla Fernando; Fernandez-Galan Rafael; del Pilar Montero-Rama Maria; Villasenor Elena; Rodriguez-Dieguez Antonio; Garcia-Vivo Daniel;

  • 作者单位

    Univ Castilla La Mancha Dept Quim Inorgan Organ &

    Bioquim Inst Reg Invest Cient Aplicada Campus Univ E-13071 Ciudad Real Spain;

    Univ Castilla La Mancha Dept Quim Inorgan Organ &

    Bioquim Ctr Innovac Quim Avanzada ORFEO CINQA Campus Univ E-13071 Ciudad Real Spain;

    Univ Castilla La Mancha Dept Quim Inorgan Organ &

    Bioquim Ctr Innovac Quim Avanzada ORFEO CINQA Campus Univ E-13071 Ciudad Real Spain;

    Univ Castilla La Mancha Dept Quim Inorgan Organ &

    Bioquim Ctr Innovac Quim Avanzada ORFEO CINQA Campus Univ E-13071 Ciudad Real Spain;

    Univ Castilla La Mancha Dept Quim Inorgan Organ &

    Bioquim Ctr Innovac Quim Avanzada ORFEO CINQA Campus Univ E-13071 Ciudad Real Spain;

    Univ Castilla La Mancha Dept Quim Inorgan Organ &

    Bioquim Ctr Innovac Quim Avanzada ORFEO CINQA Campus Univ E-13071 Ciudad Real Spain;

    Univ Granada Dept Quim Inorgan Fac Ciencias Ave Fuente Nueva S-N E-18071 Granada Spain;

    Univ Oviedo Dept Quim Organ &

    Inorgan IUQOEM E-33071 Oviedo Spain;

  • 收录信息
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 化学;无机化学;
  • 关键词

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号