Synthetic, Structural and Reactivity Studies on Early Transition Metal Chalcogenide Complexes and Supramolecules

早期过渡金属硫属化物配合物和超分子的合成、结构和反应性研究

• 批准号: 9307382
• 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: 1993
• 资助国家: 美国
• 起止时间: 1993-07-15 至 1997-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9307382&HistoricalAwards=false
• 关键词: Synthetic; Structural; Reactivity; Studies; Early

9307382 Coucouvanis Professor Coucouvanis, of the University of Michigan, will explore synthetic inorganic chemistry with support from the Inorganic, Bioinorganic, and Organometallic Chemistry Program. His efforts will concentrate on five topics, all related by the presence of metal-sulfur bonds. 1) He will explore the synthesis of thio and oxo-thio complexes of Nb and Ta with inspiration largely from analogy with the chemistry of Mo and W. A major goal will be to generate hydrido-hydrosulfido complexes by addition of H2 across M=S bonds. 2) He will develop the catalytic degradation of SO2 by use of thiomolybdate complexes. 3) He will investigate the synthesis of catecholato sulfido complexes; this will entail introduction of the catecholato group through condensations with catechol, as well as reductive couplings of catecholato complexes. 4) He will synthesize complexes having sulfate and related tetrahedral anions as bridging ligands. In this class of compounds the anions bind simultaneously to four metal centers, and are assisted by hydrogen bonding from dimethylammonium cations. 5) He will design amphiphilic supramolecules that are based on semiquinones, transition metal centers, and heterometalic M4S4 cubanes. The objective here will be to obtain "molecular reactors" for the activation of N2, O2, and CO2. %%% An important component in the advance of basic chemistry is the ever-broadening scope of molecular architecture. This is best achieved through the efforts of synthetic chemists. A particularly fertile area of synthesis is in compounds that have both metal ions and sulfur atoms. Much has been learned of the simple compounds with iron, molybdenum, and tungsten. The present research will develop the basis for the chemistry of niobium and tantalum, and it will explore the synthesis of compounds that are larger and more complex. An important objective will be to synthesize compounds that combine the properties of divergent subgroups, so as to produce "molecular reactors". This work will incorporate ideas gleaned from the study of biological enzymes. ***

9307382 Coucouvanis教授Coucouvanis，密歇根大学，将探索合成无机化学与无机，生物无机和有机化学计划的支持。 他的工作将集中在五个主题上，所有这些主题都与金属硫键的存在有关。 1)他将探索Nb和Ta的硫代和氧代硫代配合物的合成，其灵感主要来自Mo和W的化学类比。 一个主要的目标将是通过在M=S键上添加H2来产生亚甲基-氢硫基复合物。 2)他将开发利用硫代钼酸盐络合物催化降解二氧化硫。 3)他将研究儿茶酚基硫化物复合物的合成;这将需要通过与儿茶酚缩合引入儿茶酚基，以及儿茶酚基复合物的还原偶联。 4)他将合成具有硫酸根和相关四面体阴离子作为桥接配体的配合物。 在这类化合物中，阴离子同时与四个金属中心结合，并通过二甲基铵阳离子的氢键辅助。 5)他将设计基于半醌，过渡金属中心和杂金属M4 S4立方烷的两亲性超分子。 这里的目标将是获得用于活化N2、O2和CO2的“分子反应器”。 基础化学进步的一个重要组成部分是不断扩大的分子结构范围。 这是通过合成化学家的努力实现的。 一个特别丰富的合成领域是同时含有金属离子和硫原子的化合物。 关于铁、钼和钨的简单化合物，人们已经了解了很多。 目前的研究将发展铌和钽的化学基础，并将探索更大更复杂的化合物的合成。 一个重要的目标将是合成联合收割机的化合物，以生产“分子反应器”。 这项工作将结合从生物酶的研究中收集的想法。 ***