Synthetic, Structural and Reactivity Studies on Chalcogenide Complexes

硫属化物配合物的合成、结构和反应性研究

• 批准号: 8704491
• 负责人: Dimitri Coucouvanis
• 金额: $ 32.9万
• 依托单位: Regents of the University of Michigan - Ann Arbor
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1987
• 资助国家: 美国
• 起止时间: 1987-06-01 至 1990-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8704491&HistoricalAwards=false
• 关键词: Synthetic; Structural; Reactivity; Studies; Chalcogenide

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.

元素周期表中第七族的元素，包括氧、硫、硒和碲，被称为硫族。本课题主要研究金属硫化物，特别是含硫金属化合物的合成和性质。这类化合物在生物催化和工业催化中都发挥着重要的作用。金属硫化物是许多重要酶的活性中心，也是工业上重要的加氢脱硫催化剂的活性成分。这一项目有望增进对这些重要催化剂的了解，并导致设计出更有效的催化剂。该项目的目标是合成、结构表征和详细探索特定金属硫络合物的反应性。这些络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中心的结构和反应活性。B)特定的早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簇合物的结构和反应性。第一个感兴趣的领域的研究将侧重于含钼和硫的二元络合阴离子和钼/硫/氧三元阴离子的合成、结构和反应活性。用Mo/S(O)配位阴离子作为二价过渡金属离子的配位体，可以得到异金属团簇。对新的M/Mo/S(O)络合物的结构和反应活性进行了详细的研究。负载型和非负载型Mo/S(O)和M/Mo/S(O)络合物对噻吩加氢还原反应的催化效果与催化剂的化学组成有关。这些配合物有望表现出优异的反应活性，并将作为合成特定异金属簇合物的试剂。最后，Fe6S6L6团簇作为配位不饱和金属有机片段的配位体的能力将被用于合成具有MFe6S6和M2Fe6S6核心的七金属和八金属簇合物。将评估这些团簇作为小分子活化和还原模板的重要性。