Problems in Bioinorganic and Metal Cluster Chemistry

生物无机和金属簇化学问题

• 批准号: 9423830
• 负责人: Richard Holm
• 金额: $ 116.35万
• 依托单位: Harvard University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1995
• 资助国家: 美国
• 起止时间: 1995-07-01 至 1999-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9423830&HistoricalAwards=false
• 关键词: Problems; Bioinorganic; Metal; Cluster; Chemistry

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program will continue support to Dr. Richard H. Holm of the Chemistry Department, Harvard University, for research in the area of bioinorganic chemistry. Three systems will be investigated: oxygen atom transfer chemistry of molybdenum and tungsten dithiolenes, which is related to the behavior of molybdenum enzymes; hydrogen evolution from reduced nickel and formation of thioesters from nickel-acyls and thiols, which are studies relevant to the behavior of hydrogenase and carbon monoxide dehydrogenase; and binuclear iron-copper bridged molecular assemblies related to the binuclear sites of heme-copper oxidases. Kinetics and other aspects of these processes will be examined to provide descriptions of reaction pathways that may be feasible in enzymatic reactions. In addition, low-temperature syntheses of metal clusters containing chalcogenides or chalcohalides will be developed. Enzymatic reactions provide rapid low-energy routes to reactions important not only in biological systems, but also in synthesis of important organic and inorganic chemicals. By investigating the detailed mechanism of fundamental reactions involving oxygen atom transfer, oxidation-reduction, and hydrogen transfer, Dr. Holm may elucidate spatial and steric requirements useful for the development of new synthetic routes, as well as increase understanding of biological action

无机化学、生物无机化学和金属有机化学项目的这一奖项将继续支持哈佛大学化学系的理查德·H·霍尔姆博士在生物无机化学领域的研究。三个体系将被研究：钼和钨的二硫烯的氧原子转移化学，它与钼酶的行为有关；还原镍的放氢和镍-酰基和硫醇形成硫酯的研究，这与氢酶和一氧化碳脱氢酶的行为有关；以及与血红素-铜氧化酶的双核位置相关的双核铁-铜桥联分子组合。将研究这些过程的动力学和其他方面，以提供在酶反应中可能可行的反应途径的描述。此外，还将开发含硫化物或硫卤化物的金属簇合物的低温合成。酶反应为反应提供了快速、低能量的途径，这些反应不仅在生物系统中很重要，而且在重要的有机和无机化学品的合成中也是如此。通过研究包括氧原子转移、氧化还原和氢转移在内的基本反应的详细机制，霍尔姆博士可能阐明有助于开发新的合成路线的空间和空间要求，以及增加对生物作用的理解。