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

密歇根大学的Coucouvanis教授将在无机、生物无机和有机金属化学项目的支持下探索合成无机化学。他的努力将集中在五个主题上，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，灵感主要来自Mo和w的化学类比。主要目标是通过在M=S键上加成H2来生成氢-氢硫代配合物。2)开发硫钼酸盐配合物催化降解SO2的研究。3)研究儿茶酚硫配合物的合成；这将需要通过与儿茶酚的缩合来引入儿茶酚基团，以及儿茶酚复合物的还原偶联。他将合成以硫酸盐和相关的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，并由二甲基铵离子形成的氢键辅助。5)他将设计基于半醌、过渡金属中心和异金属m444立方烷的两亲性超分子。这里的目标是获得活化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分子结构的范围不断扩大。这最好通过合成化学家的努力来实现。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。本研究将为铌和钽的化学性质奠定基础，并将探索更大更复杂化合物的合成。一个重要的目标将是合成结合不同亚基团性质的化合物，从而产生“分子反应器”。这项工作将结合从生物酶研究中收集到的想法。＊＊＊

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. ***