...
  • 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 >Hydrogenation of titanocene and zirconocene bis(trimethylsilyl)acetylene complexes
【24h】

Hydrogenation of titanocene and zirconocene bis(trimethylsilyl)acetylene complexes

机译：钛烯和锆醚双（三甲基甲硅烷基）乙炔配合物的氢化

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

Reactions following the addition of dihydrogen under maximum atmospheric pressure to bis(trimethylsilyl)acetylene (BTMSA) complexes of titanocenes, [(eta(5)-C5H5-nMen)(2)Ti(eta(2)-BTMSA)] (n = 0, 1, 3, and 4) (1A-1D), and zirconocenes, [(eta(5)-C5H5-nMen)(2)Zr(eta(2)-BTMSA)] (n = 2-5) (4A-4D), proceeded in diverse ways and, depending on the metal, afforded different products. The former complexes lost, in all cases, their BTMSA ligand via its hydrogenation to bis-1,2-(trimethylsilyl)ethane when reacted at 80 degrees C for a prolonged reaction time. For n = 0, 1, and 3, the titanocene species formed in situ dimerised via the formation of fulvalene ligands and two bridging hydride ligands, giving known green dimeric titanocenes (2A-2C). For n = 4, a titanocene hydride [(eta(5)-C5HMe4)(2)TiH] (2D) was formed, similarly to the known [(eta(5)-C5Me5)(2)TiH] (2E) for n = 5; however, in contrast to this example, 2D in the absence of dihydrogen spontaneously dehydrogenated to the known Ti(III)-Ti(III) dehydro-dimer [{Ti(eta(5)-C5HMe4)(mu-eta(1):eta(5)-C5Me4)}(2)] (3B). This complex has now been fully characterised via spectroscopic methods, and was shown through EPR spectroscopy to attain an intramolecular electronic triplet state. The zirconocene-BTMSA complexes 4A-4D reacted uniformly with one hydrogen molecule to give Zr(IV) zirconocene hydride alkenyls, [(eta(5)-C5H5-nMen)(2)ZrH{C(SiMe3)=CH(SiMe3)}] (n = 2-5) (5A-5D). These were identified through their H-1 and C-13 NMR spectra, which show features typical of an agostically bonded proton, -CH(SiMe3). Compounds 5A-5D formed equilibria with the BTMSA complexes 4A-4D depending on hydrogen pressure and temperature.
机译：下最大大气压加入二氢到双以下反应（三甲基甲硅烷基）乙炔（BTMSA）二茂钛络合物，[（ETA（5）-C 5 H 5-NMEN）（2）的Ti（ETA（2）-BTMSA）]（N = 0,1，3和4）（1A〜1D），和二茂锆，[（ETA（5）-C 5 H 5-NMEN）（2）的Zr（ETA（2）-BTMSA）]（N = 2-5）（图4A-4D），进行以不同的方式，并且根据金属，得到不同的产品。当在80℃下在延长的反应时间下反应，前者配合物丢失，在所有情况下，它们的配体BTMSA通过其氢化为双 - 1,2-（三甲基硅烷基）乙烷。对于n = 0，1和3，在原位形成二茂钛物种通过富瓦烯配体和两个桥接配体氢化物的形成二聚化，得到公知的绿色二聚体二茂钛（2A-2C）。对于n形成= 4，二茂钛氢化物[（ETA（5）-C5HMe4）（2）TIH]（2D）中，类似于已知的[（ETA（5）-C5Me5）（2）TIH]（2E），用于N = 5;然而，相比于本实施例中，2D在不存在自发二氢脱氢已知的Ti（III）-Ti（III）的脱氢二聚物[{钛（ETA（5）-C5HMe4）（MU-ETA（1）： ETA（5）-C5Me4）}（2）]（3B）。这种复杂的现已通过光谱学方法被完全表征，并且通过EPR光谱显示出达到分子内的电子三重态。锆茂-BTMSA络合物4A-4D与一个氢分子均匀地进行反应，得到的Zr（IV）锆氢化烯基，[（ETA（5）-C 5 H 5-NMEN）（2）{ZRH C（SiMe3）= CH（SiMe3）} ]（N = 2-5）（5A-5D）。这些是通过它们的H-1和C-13 NMR谱，其示出了设有一个典型结合agostically质子，-CH（SiMe3）的鉴定。化合物5A-5D与BTMSA形成平衡络合物4A-4D根据氢压力和温度。

著录项

  • 来源
  • 作者

    Pinkas Jiri; Gyepes Robert; Cisarova Ivana; Kubista Jiri; Horacek Michal; Zilkova Nadezda; Mach Karel;

  • 作者单位

    Czech Acad Sci Vvi J Heyrovsky Inst Phys Chem Dolejskova 3 Prague 18223 8 Czech Republic;

    J Selye Univ Fac Educ Dept Chem Bratislayska Cesta 3322 Komarno 94501 Slovakia;

    Charles Univ Prague Dept Inorgan Chem Hlavova 2030 Prague 12840 2 Czech Republic;

    Czech Acad Sci Vvi J Heyrovsky Inst Phys Chem Dolejskova 3 Prague 18223 8 Czech Republic;

    Czech Acad Sci Vvi J Heyrovsky Inst Phys Chem Dolejskova 3 Prague 18223 8 Czech Republic;

    Czech Acad Sci Vvi J Heyrovsky Inst Phys Chem Dolejskova 3 Prague 18223 8 Czech Republic;

    Czech Acad Sci Vvi J Heyrovsky Inst Phys Chem Dolejskova 3 Prague 18223 8 Czech Republic;

  • 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