Synthesis and Chemistry of Zintl-Transition Metal Clusters

无机化学、生物无机化学和金属有机化学计划中的这个项目涉及同时包含过渡金属和主族原子的簇合物，特别是所谓的锌化合物。将发展这类簇合物的合成和化学，以了解这些化合物中的基本成键模式。特别令人感兴趣的是产生了与锌簇阴离子和相关锌相具有相似之处的离散络合物。经典的含主族原子的过渡金属羰基将被CO等配体处理，它们的还原化学将沿着对一些已知的此类簇合物成功的路线进行探索。努力将集中在重元素，即Tl，Pb和Bi.计划包括探索直接使用各种类型的合金进行离散簇合成，包括一些锌相和主族/过渡金属合金。作为高核度物质的来源，我们将考察铋-铁酮基团簇阴离子和铊-铁酮基团簇阴离子的反应。化合物将通过单晶X射线衍射、磁性测量、电子显微镜以及适当的核磁共振、莫斯鲍尔和红外光谱进行表征。该项目中正在研究的反应对固体化学、材料科学以及催化都有很大的影响。

This project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is concerned with cluster compounds containing both transition metals and main group atoms, particularly the so-called Zintl compounds. The synthesis and chemistry of such cluster complexes will be developed to understand the fundamental bonding patterns in these compounds. Of particular interest is the creation of discrete complexes which have similarities to the Zintl cluster anions and related Zintl phases. Classical main group atom-containing transition metal carbonyls will be treated with ligands such as CO, and their reduction chemistry will be explored following routes which have been successful for some known clusters of this type. Efforts will center around the heavy elements, namely Tl, Pb and Bi. Plans include exploration of the direct use of various types of alloys for discrete cluster synthesis, including some of the Zintl phases and main group/transition metal alloys. Reactions of bismuth-iron carbonyl and of thallium-iron carbonyl cluster anions will be examined as sources of high nuclearity substances. Compounds will be characterized by single-crystal X-ray diffraction, magnetic measurements, electron microscopy and NMR, Moessbauer and IR spectroscopies as appropriate. The reactions under investigation in this project have strong implications for solid state chemistry and materials science as well as catalysis.