Discrete and Extended Arrays of Main Group Elements and Transition Metals

有了这个奖项，无机，生物无机和有机化学计划支持的研究，由Dallon H。惠特迈尔，莱斯大学化学系，关于主族元素（E）和过渡金属（M）的簇。新的技术将用于合成具有新的成键和反应特性的大的、新颖的E-M簇合物。重p区元素由于其尺寸、刘易斯酸碱性质、金属特性和相对论效应，经常形成不寻常的化合物。 高压合成将在专门设计的单元中通过红外光谱法进行监测。将与法国雷恩大学的Jean-Yves Saillard博士合作分析这种结合。将使用X射线衍射、NMR和IR光谱以及磁化率对化合物进行表征。此外，通过原位分析羰基化和加氢反应的动力学和机理，研究了M3 E簇合物家族的催化活性。主族元素的作用特别重要。本研究将使用高压反应器来监测团簇组成、反应气体压力、溶剂和离子配对对团簇稳定性的影响。主族元素与过渡金属的相互作用在化学、材料科学和催化中具有重要意义。含有p-和d-区元素的合金具有有趣的电子和磁性。了解这些不同的元素如何形成结构，键合和反应对于表征离散化合物以及扩展的固态相非常重要。 这是第一次，这些元素形成大团簇和它们在催化反应中的行为将在真实的时间详细研究。 研究生和本科生将学习如何整合实验和理论结果。

With this award, the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research by Kenton H. Whitmire, Department of Chemistry, Rice University, on clusters of main group elements (E) and transition metals (M). New techniques will be used to synthesize large, novel E-M cluster compounds with new bonding and reactivity characteristics. Heavy p-block elements often form unusual compounds because of their size, Lewis acid-base properties, metallic character and relativistic effects. The high-pressure synthesis will be monitored by infrared spectroscopy in a specially designed cell. The bonding will be analyzed in collaboration with Dr. Jean-Yves Saillard of the Universite de Rennes, France. The compounds will be characterized using x-ray diffraction, NMR and IR spectroscopies, and magnetic susceptibility. In addition, the catalytic activity of the M3E family of cluster compounds will be studied by in situ analysis of the kinetics and mechanism of carbonylation and hydrogenation reactions. The role of the main group element is of particular interest. The high-pressure reactor used in the synthetic studies will be used in this investigation to monitor the effects of cluster composition, reactant gas pressure, and solvent and ion pairing on cluster stability.The interaction of main group elements and transition metals is important in chemistry, materials science and catalysis. Alloys containing elements of the p- and d- blocks have interesting electronic and magnetic properties. Understanding how these different elements form structures, bond, and react is important in characterizing discrete compounds and also in extended solid state phases. For the first time, both formation of these elements into large clusters and their behavior in catalytic reactions will be studied in detail in real time. Graduate and undergraduate students would learn how to integrate experimental and theoretical results.