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Synthesis and characterization of high nuclearity bimetallic group 8-group 10 transition metal cluster complexes.

机译:高核双金属8族-10族过渡金属簇配合物的合成与表征。

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摘要

In past years bimetallic nanoparticle catalysts have been shown to exhibit superior catalytic properties, due to the presence of different metals such that one metal performs a certain role in a catalytic cycle and the other performs another function. Our goal was to synthesize bimetallic cluster complexes containing cheap metals for the application in heterogeneous catalysis. We have reported the reaction of Fe5(C)(CO)15with Ni(COD) 2, in acetonitrile solvent to afford the nickel-iron complex Fe 5(C)Ni(NCMe)(CO)15. In addition, some chemistry with this compound was studied which gave new Fe-Ni carbide clusters with varying Fe-Ni ratios. Similar chemistry was observed with the reaction of Ru5(C)(CO) 15 with Ni(COD)2. Electronic unsaturation in transition metal complexes is induced by bulky ligands. The bulky ligands shield the metal center from the approach of large molecules, leaving enough room for the selective approach of small molecules. Bulky ligands such as phosphines, stananes, germanes and N-heterocyclic carbenes stabilize the reactive intermediates of transition metal complexes. Based on this approach, we have synthesized Ru-Ge cluster complexes from the reaction of bulky tertiary butyl germane, ButGeH 3 with ruthenium carbonyl complexes. We have also synthesized Ru-Pt bimetallic transition metal cluster complexes with bulky N-heterocyclic carbene ligand. All the new compounds were structurally characterized by single-crystal X-ray diffraction analyses.
机译:在过去的几年中,由于存在不同的金属,双金属纳米颗粒催化剂已显示出优异的催化性能,使得一种金属在催化循环中起特定作用,而另一种发挥另一种功能。我们的目标是合成包含廉价金属的双金属簇络合物,用于多相催化。我们已经报道了Fe5(C)(CO)15与Ni(COD)2在乙腈溶剂中的反应,得到镍铁络合物Fe 5(C)Ni(NCMe)(CO)15。另外,研究了该化合物的化学反应,得到了具有不同铁镍比的新铁镍碳化物簇。 Ru5(C)(CO)15与Ni(COD)2的反应观察到相似的化学反应。过渡金属配合物中的电子不饱和度是由庞大的配体引起的。笨重的配体使金属中心免受大分子的干扰,从而为小分子的选择性接近留出了足够的空间。庞大的配体(例如膦,锡烷,锗烷和N-杂环卡宾)可稳定过渡金属配合物的反应中间体。基于这种方法,我们从大叔丁基锗烷ButGeH 3与羰基钌络合物的反应中合成了Ru-Ge簇络合物。我们还合成了具有庞大的N-杂环卡宾配体的Ru-Pt双金属过渡金属簇络合物。所有新化合物都通过单晶X射线衍射分析进行了结构表征。

著录项

  • 作者

    Saha, Sumit.;

  • 作者单位

    University of Miami.;

  • 授予单位 University of Miami.;
  • 学科 Chemistry Molecular.;Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2013
  • 页码 160 p.
  • 总页数 160
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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