Fundamental Processes in Metal Cluster Chemistry

金属簇化学的基本过程

• 批准号: 9016495
• 负责人: Edward Rosenberg
• 金额: $ 16.5万
• 依托单位: The University Corporation, Northridge
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-12-01 至 1994-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9016495&HistoricalAwards=false
• 关键词: Fundamental; Processes; Metal; Cluster; Chemistry

This award in the Inorganic, Bioinorganic, and Organometallic Program supports the continued work of Dr. Edward Rosenberg of the Chemistry Department, California State University at Northridge, for the investigation of the role of ligand mobility in metal cluster reactions. In particular, Rosenberg will study the transfer of hydrogen between oxygen or nitrogen and metal carbonyl cluster systems and investigate the source of the kinetic isotope effect previously observed for this reaction. He will also study substitution and addition reactions of some osmium and ruthenium clusters containing face-capping nitrogen ligands in order to elucidate the role of stereochemical nonrigidity in this reaction. These studies will potentially provide new insights into the mechanism of activation by metal surfaces in catalysis. One mechanism for protonation consistent with the observed kinetic isotope effect is proton tunneling, but an alternative mechanism is intermolecular transfer. Low temperature protonation reactions of ruthenium carbonyls by deuterated acid will be studied in order to determine the extent to which proton transfer is intra- or intermolecular. In related work, a series of dinuclear rhenium compounds will be studied to see if cluster fluxionality can result in a symmetrical hydrogen transfer intermediate, a usual requirement for proton tunneling. For the stereochemical nonrigidity studies, a trinuclear ruthenium cluster will be reacted with diazomethane and its deuterated analog to investigate the unexpected room temperature oxidative addition of CH in this reaction and the involvement, if any, of the bridging hydride.

该奖项在无机，生物无机和有机化学 该计划支持爱德华·罗森伯格博士的继续工作， 加州州立大学化学系， Northridge，用于研究配体的作用 金属簇反应中的迁移率。 特别是罗森伯格 将研究氢在氧或氮之间的转移 和金属羰基簇合物系统，并调查来源 之前观察到的动力学同位素效应 反应 他还将学习替代和添加 某些锇和钌簇合物的反应， 面封氮配体，以阐明的作用， 在这个反应中立体化学的非刚性。 这些研究 将可能为研究 催化中金属表面的活化作用。 质子化的一种机制与观察到的一致 动力学同位素效应是质子隧穿，但另一种选择是 机制是分子间转移。 低温 羰基钌与氘代酸的质子化反应 将进行研究，以确定 质子转移是分子内或分子间的。 在相关工作中， 一系列的双核化合物将被研究， 如果团簇流动性可以导致对称氢 转移中间体，通常需要质子 隧道 对于立体化学非刚性研究， 三核钌簇合物将与重氮甲烷反应 和它的氘代类似物来研究这个意想不到的房间 在该反应中，CH的温度氧化加成和 如果有的话，桥氢化物的参与。