Small-to-Gigantic Transition Metal Clusters

从小到大的过渡金属簇

• 批准号: 9013059
• 负责人: Lawrence Dahl
• 金额: $ 51.4万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-06-01 至 1993-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9013059&HistoricalAwards=false
• 关键词: Small; Gigantic; Transition; Metal; Clusters

The focus of this project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is the the chemistry of transition metal cluster compounds. The project involves the synthesis of new cluster compounds, characterization of their structures and bonding, and studies of their electrochemical and chemical reactivity patterns. A major objective of the research is to provide a unified correlation, based on molecular orbital theory, between molecular geometries and electronic configurations for various kinds of metal clusters, many of which gain and/or lose electrons without rupture of their atomic frameworks. Transition metal cluster compounds comprise an important class of industrial catalysts, and some very large clusters are of intense current interest because they display anomalous magnetic behavior ("quantum size" effects) not seen in small clusters or bulk solids. The main thrust of the project will be the synthesis, isolation and characterization of platinum, nickel and mixed-metal cluster anions, with emphasis on the design of rational synthetic routes to high-nuclearity metal clusters and the development of appropriate separation techniques to enable the isolation and crystallization of pure species for structural and physical studies. Another overall goal is to bridge the gap between discrete and extended solid-state clusters via appropriate oligomerization/condensation reactions. New metal clusters will be synthesized which contain main-group ligands with S, Se, Te, N, P, As or Sb atoms. New metal phosphorus clusters will be prepared by the photolysis of molecular tetraphosphorus. An attempt will be made to use the parameter-free Fenske-Hall model to provide a quantitative electronic basis for the results of crystallographic and spectrocopic analyses of small metal clusters.

该项目的重点是无机，生物无机和 有机化学计划是化学的 过渡金属簇合物。该项目涉及 新型原子簇化合物合成、表征 结构和键合，以及它们的电化学研究 和化学反应模式的一个主要目标 研究是提供一个统一的相关性，基于 分子轨道理论，介于分子几何和 各种金属簇的电子构型， 其中许多获得和/或失去电子而不破裂， 原子框架。过渡金属簇合物 包括一类重要的工业催化剂，并且一些 非常大的集群是目前的强烈兴趣，因为 它们显示出异常的磁性行为（“量子尺寸”）， 效应）在小团簇或大块固体中看不到。 该项目的主旨将是综合，隔离， 铂、镍和混合金属的特性 簇阴离子，重点是合理的设计 合成路线，以高核性金属簇和 开发适当的分离技术， 分离和结晶结构纯物质 和物理研究。 另一个总体目标是弥合 离散和扩展固态团簇之间的间隙， 合适的低聚/缩合反应。新金属 将合成含有主族配体的簇 具有S、Se、Te、N、P、As或Sb原子。新金属磷 团簇将通过分子的光解来制备， 四磷将尝试使用 无参数Fenske-Hall模型提供了一个定量的 晶体学结果的电子基础， 小金属簇的光谱分析。