Discrete and Extended Arrays of Main Group Elements and Transition Metals

该项目在无机、生物无机和金属有机化学计划中，涉及同时包含过渡元素(M)和重非过渡金属元素(E)的多核化合物的合成和物理和化学表征，作为簇合物框架的组成部分。要遵循的合成策略包括1)取代现有簇合物中的E-结合卤化物，2)金属铋化合物中均溶的铋-碳键断裂为用于偶合反应的活性碎片，3)现有稳定的小簇合物上的氧化还原反应产生可耦合成较大碎片的活性碎片，4)已知的第9和10族金属簇合物与由铋氢化物热分解产生的“裸”铋原子反应，5)铋和锑锌离子与具有容易取代配体的过渡金属化合物的反应，以及6)铋合金在配体存在下的阴极溶解以捕获预期的小阴离子簇合物。越来越清楚的是，含有过渡金属和非金属元素的合金和化合物具有有趣的和可能具有重要技术意义的电子和磁性，以及独特的催化性能。然而，过渡金属和重非金属元素之间的成键作用的基本方面几乎没有受到关注，因此目前无法解释和预测性质。该项目的主要目标是通过研究含有过渡金属原子和非金属元素之间键的簇合物，获取有关这些元素相互作用的信息。这些团簇的分解反应也可能导致具有有用性能的新合金。

This project, in the Inorganic, Bioinorganic and Organometallic Chemistry Program, is concerned with the synthesis, and the physical and chemical characterization of polynuclear compounds that contain both transition elements (M) and heavy non-transition metal elements (E) as an integral part of the cluster framework. Synthetic strategies to be followed include 1) substitution of E-bound halide in existing cluster compounds, 2) homolytic bismuth-carbon bond cleavage in metallated bismuth compounds to reactive fragments for coupling reactions, 3) redox reactions on existing stable small clusters to generate reactive fragments that may couple to give larger fragments, 4) reactions of known Group 9 and 10 metal clusters with "bare" bismuth atoms generated by thermal decomposition of bismuth hydride, 5) the reactions of bismuth and antimony Zintl ions with transition metal compounds that have readily substituted ligands, and 6) cathodic dissolution of bismuth alloys in the presence of ligands to trap the anticipated small anionic clusters. It is increasingly clear that alloys and compounds that contain transition metals and non-metallic elements have interesting and potentially technologically important electronic and magnetic properties, and unique catalytic properties. However, the fundamental aspects of the bonding interactions between transition metals and heavy non-metallic elements has received little attention so that interpretation and prediction of properties are currently impossible. This project has as its primary objective the acquisition of information concerning interactions of such elements through the study of cluster compounds that contain bonds between transition metal atoms and non-metallic elements. Decomposition reactions of these clusters may also lead to new alloys with useful properties.