Chemistry of Polynuclear Metal Carbonyls

本文的研究方向是有机金属化学的总体方向和金属团簇化学的具体方向。该研究有望对金属簇在有机化合物的合成和转化中如何作为催化剂发挥作用提供更清晰的理解。研究将集中在金属团簇化学的两个领域。第一个领域将讨论金属团簇的反应机制，特别是在均相催化中的反应机制。将使用两种方法来优化整个催化循环中簇保持完整的可能性。第一个将涉及使用卤化物和假卤化物在温和条件下激活简单羰基簇。第二种方法将涉及使用mu-3-NR配体将簇内的金属强结合在一起，以便在更剧烈的条件下研究反应。金属团簇化学的第二个一般领域是合成低聚物和团簇聚合物。集群将与各种有机连接基团连接在一起，以提供不同类型的结构。低聚物的氧化还原化学将被探索，因为期望通过部分氧化获得的混合价态的不寻常的电子性质。

The proposed research is in the general area of organometallic chemistry and in the specific area of metal cluster chemistry. The research is expected to provide a clearer understanding of how metal clusters function as catalysts in the synthesis and transformation of organic compounds. The research will focus on two areas of metal cluster chemistry. The first area will address the reaction mechanisms of metal clusters, particularly in homogeneous catalysis. Two approaches will be used to optimize the likelihood that the clusters will remain intact throughout the catalytic cycle. The first will involve the use of halides and pseudohalides to activate simple carbonyl clusters under mild conditions. The second approach will involve the use of mu-3-NR ligands to bind together strongly the metals within the cluster, so that reactions under more vigorous conditions may be studied. The second general area of metal cluster chemistry to be addressed is the synthesis of oligomers and polymers of clusters. Clusters will be linked together with a variety of organic linking groups to provide different types of structures. The redox chemistry of the oligomers will be explored, since unusual electronic properties are expected for the mixed valence species obtained by partial oxidation.