Problems in Bioinorganic and Metal Cluster Chemistry

无机、生物无机和有机金属化学项目的这一奖项将继续支持哈佛大学化学系的Richard H. Holm博士在生物无机化学领域的研究。研究了三种体系：钼、钨二噻吩的氧原子转移化学，这与钼酶的行为有关；还原镍的析氢和镍酰基和硫醇形成硫酯，这是与氢化酶和一氧化碳脱氢酶行为相关的研究；双核铁铜桥接分子组合与血红素铜氧化酶的双核位点有关。动力学和这些过程的其他方面将进行检查，以提供在酶促反应中可能可行的反应途径的描述。此外，低温合成含硫属化合物或硫化物的金属团簇也将得到发展。酶促反应不仅为生物系统中重要的反应提供了快速的低能途径，而且在重要的有机和无机化学品的合成中也很重要。通过研究涉及氧原子转移、氧化还原和氢转移的基本反应的详细机制，霍尔姆博士可能会阐明空间和空间要求，这对开发新的合成路线有用，并增加对生物作用的理解

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