Synthetic, Structural and Reactivity Studies on Chalcogenide Complexes

元素周期表第七族的元素，包括氧、硫、硒和碲，被称为硫原。本课题主要研究金属硫族化合物的合成及其性质，特别是含硫金属化合物。这类化合物在生物催化和工业催化中发挥着重要作用。金属硫化物构成了许多重要酶的活性位点，也是工业上重要的加氢脱硫催化剂的活性成分。该项目有望加深对这些重要催化剂的了解，并设计出更高效的催化剂。本项目的目标是合成、结构表征和详细探索特定金属硫配合物的反应性。这些配合物有望帮助我们理解a)工业上重要的加氢脱硫（HDS）反应催化剂中金属硫活性位点的结构和反应活性。b)特定的早期过渡金属硫配合物的结构和反应性；c)一类新的异核M/Fe/S簇的结构和反应性。第一个兴趣领域的研究将侧重于含钼和硫的二元复合阴离子和钼/硫/氧三元阴离子的合成、结构和反应性。用Mo/S(O)配合阴离子作为二价过渡金属离子的配体，可以得到异质金属簇。详细研究了新型M/Mo/S(O)配合物的结构和反应性。负载型或非负载型Mo/S(O)和M/Mo/S(O)配合物作为噻吩HDS催化剂的有效性与Zr/S、Nb/S和镧系元素/S配合物的化学性质有关。这些配合物有望显示出特殊的反应活性，并将作为合成特定异金属团簇的试剂。最后，利用Fe6S6L6簇作为配体的能力，可以合成具有MFe6S6和M2Fe6S6核的七金属和八金属簇。这些簇作为小分子活化和还原模板的重要性将被评估。

The elements of Group Seven of the Periodic Table, including oxygen, sulfur, selenium and tellurium, are known as the chalcogens. This research project is concerned with the synthesis and properties of metal chalcogenides, especially compounds of metals with sulfur. Such compounds play important roles both in biological and industrial catalysis. Metal Sulfides constitute the active sites of a number of important enzymes and are the active ingredient in the industrially important hydrodesulfurization catalysts. This project is expected to enhance understanding of these important catalysts and lead to the design of more efficient catalysts. The goals of this project are to synthesize, structurally characterize and explore in detail the reactivities of specific metal- sulfur complexes. These complexes are expected to assist in our understanding of a) The structures and reactivity of the metal sulfur active sites in the industrially important hydrodesulfurization (HDS) reaction catalysts. b) The structures and reactivity of specific early transition metal sulfur complexes and c) The structures and reactivities of a new class of heteronuclear M/Fe/S clusters. Research in the first area of interest will place emphasis in the synthesis, structure and reactivity of the binary complex anions containing molybdenum and sulfur and ternary molybdenum/sulfur/oxygen anions. Heterometallic clusters will be obtained using the Mo/S(O)complex anions as ligands for divalent transition metal ions. The structures and reactivity of the new M/Mo/S(O) complexes will be studied in detail. The effectiveness of supported or unsupported Mo/S(O) and M/Mo/S(O) complexes as catalysts for the HDS of thiophene concerns the chemistry of Zr/S, Nb/S and Lanthanides/S complexes. These complexes are expected to display exceptional reactivity, and will serve as reagents for the synthesis of specific heterometallic clusters. Finally the ability of the Fe6S6L6 clusters to serve as ligands for coordinatively unsaturated organometallic fragments, will be utilized for the synthesis of hepta- and octametallic clusters with the MFe6S6 and M2Fe6S6 cores. The importance of these clusters as templates for the activation and reduction of small molecules will be evaluated.