Discrete and Extended Arrays of Main Group Elements and Transition Metals

主族元素和过渡金属的离散和扩展阵列

• 批准号: 9408613
• 负责人: Kenton Whitmire
• 金额: --
• 依托单位: William Marsh Rice University
• 依托单位国家: 美国
• 项目类别: Continuing grant
• 财政年份: 1994
• 资助国家: 美国
• 起止时间: 1994-08-01 至 1999-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9408613&HistoricalAwards=false
• 关键词: Discrete; Extended; Arrays; Main; Group

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.

该项目属于无机、生物无机和有机金属化学计划，涉及包含过渡元素 (M) 和重非过渡金属元素 (E) 作为组成部分的多核化合物的合成和物理和化学表征的集群框架。 遵循的合成策略包括1）取代现有簇化合物中的E结合卤化物，2）金属化铋化合物中的均解铋碳键断裂为反应片段以进行偶联反应，3）现有稳定小簇上的氧化还原反应以产生反应活性碎片可能耦合产生更大的碎片，4) 已知第 9 族和第 10 族金属簇与由铋热分解产生的“裸”铋原子的反应氢化物，5) 铋和锑 Zintl 离子与具有容易取代的配体的过渡金属化合物的反应，以及 6) 在配体存在下阴极溶解铋合金以捕获预期的小阴离子簇。 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且具有潜在技术重要性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键合相互作用的基本方面很少受到关注，因此目前不可能解释和预测性能。 该项目的主要目标是通过研究包含过渡金属原子和非金属元素之间键的簇化合物来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产生具有有用特性的新合金。