Small to Gigantic Metal Clusters

这个无机、生物无机和有机金属化学项目的奖项为威斯康星大学麦迪逊分校化学系的Lawrence F. Dahl博士对过渡金属羰基簇化合物的研究提供了持续的支持。一个主要目标是为各种金属团簇提供分子几何形状和电子构型之间的统一关联，其中许多团簇在不破坏其原子框架的情况下获得或失去电子。研究将集中在两个方面：1)高核铂、镍和混合金属羰基簇的分离、结构测定和物理化学表征；2)小型富电子金属簇的合成、立体化学键分析和电化学反应性。合理的制备大簇的方法和适当的分离技术，以分离和结晶纯物种进行表征仍有待发展。除了确定这些配合物的结构外，还将研究它们的磁性能和一氧化碳吸附模式。还将研究金属团簇与主基团试剂的反应性，这可能有助于稳定物种。将尝试分离具有新型键合特征的金属磷化物和金属砷团簇。可以使用标准化学方法表征的大型金属团簇可能是理解固体金属表面或晶格碎片行为的有用模型，这通常用于催化。特别令人感兴趣的是反应性特性和电子特性。这项工作可能会产生有效的催化剂材料，或改善目前工业使用的反应条件或催化材料的表面制备。＊＊＊

9310428 Dahl This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program provides continued support for research on transition metal carbonyl cluster compounds by Dr. Lawrence F. Dahl of the Chemistry Department, University of Wisconsin-Madison. A major goal is to provide a unified correlation between molecular geometries and electronic configuration for various kinds of metal clusters, many of which gain or lose electrons without rupture of their atomic frameworks. Research will be focused in two areas: 1) isolation, structural determination, and physical-chemical characterization of high nuclearity platinum, nickel, and mixed-metal carbonyl clusters; and 2) synthesis, stereochemical-bonding analysis, and electrochemical reactivity of small electron-rich metal clusters. Rational methods for preparing large clusters and appropriate separation techniques to isolate and crystallize pure species for characterization remain to be developed. In addition to determining the structure of these complexes, their magnetic properties and modes of carbon monoxide adsoption will be investigated. The reactivity of metal clusters with main group reagents, which may be able to stabilize the species, will also be studied. Attempts will be made to isolate metal phosphide and metal arsenic clusters with novel bonding features. %%% Large metal clusters that can be characterized using standard chemical methods may be useful models for understanding the behavior of solid metal surfaces or lattice fragments, which are often used in catalysis. Of particular interest are reactivity characteristics and electronic features. The work may result in materials that are effective as catalysts or in the improvement of reaction conditions or surface preparation of catalytic materials currently in industrial use. ***