Sulfur and Ylide Coordination Compounds - Mono-, Bi- and Trimetallic Organometallic Reactions and Structures

铜、银、金、镍、钯和铂的金属化合物是非常重要的催化剂，作为具有良好磁性或电性的固体正变得越来越重要。这一研究项目的重点是这些金属的新化合物的合成和表征，有望产生新的催化剂和有趣的新固体材料，如一维导体。这项研究还可能提供对酶中的金属硫簇以及金与生物组织结合方式的更好理解。过渡金属离子和配位体键对配位化合物结构和反应活性的影响概括地描述了这项工作。特别是，重点将放在过渡金属化合物上，主要是含有硫和叶立德配体的镍和铜三元元素。重要的具体研究涉及M-M、C-S、S-S和M-S键的形成和断裂，以及所产生的过渡金属有机金属物种的性质。使用X射线结晶学的结构研究构成了这项工作的重要部分。关于第二金属中心在影响具有8、9或10个d电子的金属中心的氧化加成、还原消除反应化学中的作用的新认识对这一提议特别感兴趣。小分子跨M-M键的加成也有待探索。含有Au……Pt...Au线性排列的新的异三金属物种，由于其在固态中的氧化性质和线性堆积排列，将受到特别的研究。

Compounds of the metals copper, silver, gold, nickel, palladium and platinum are very important catalysts and are becoming increasingly important as solids with desirable magnetic or electrical properties. This research project, the focus of which is the synthesis and characterization of new compounds of these metals, is expected to result in new catalysts and interesting new solid materials, such as one-dimensional conductors. The research may also provide a better understanding of the metal-sulfur clusters in enzymes and of the way in which gold binds to biological tissues. The influence of transition metal ions and ligand bonding on the structure and reactivity of coordination compounds broadly describes this work. In particular, the focus will be on transition metal compounds primarily of the nickel and copper triad elements which contain sulfur and ylide ligands. Specific studies of importance relate to M-M, C-S, S-S and M-S bond formation and rupture, and the properties of the transition-metal organometallic species produced. Structural studies using X-ray crystallography form an important part of this work. Of special interest in this proposal is the development of new understanding concerning the role of a second metal center in influencing the oxidative-addition, reductive-elimination reaction chemistries at metal centers with 8, 9 or 10 d-electrons. The addition of small molecules across the M-M bond also is to be explored. The new heterotrimetallic species containing a linear Au.....Pt.....Au arrangement will receive special study due to its oxidation properties and linear stacked arrangement in the solid state.