Mechanistic Chemistry of Transition Metal Oxygen and Oxo Complexes

过渡金属氧和氧配合物的机理化学

• 批准号: 9625349
• 负责人: James Espenson
• 金额: $ 28.5万
• 依托单位: Iowa State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1996
• 资助国家: 美国
• 起止时间: 1996-06-01 至 2000-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9625349&HistoricalAwards=false
• 关键词: Mechanistic; Chemistry; Transition; Metal; Oxygen

Dr. James Espenson and Dr. Andreja Bakac of the Department of Chemistry, Iowa State University, are supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for studies to develop a molecular level understanding of oxygen atom transfer. They will probe the mechanisms of oxygen atom transfer reactions of transition metal oxygen and oxo complexes. The studies include the use of the complex, methylrhenium dioxide (MDO), as a prototype oxygen atom acceptor, and inorganic oxyanions and transition metal oxo complexes as oxygen donors. Kinetic and thermodynamic determinations will be carried out to construct a scale of oxygen atom transfer reactivities on the basis of the Marcus equation. The effects of hydrogen bonding on the stability of superoxometal complexes will be studied using deuterium isotope effects, and the chemistry of superoxo and oxo ions of biologically relevant chromium complexes will be investigated. Chemical reactions in which oxygen atoms are transferred from one metal to another or from metals to non-metals are fundamental to many biological and industrial processes. However, advances in this area are currently hindered by the lack of a fundamental understanding of these processes. In this project, Espenson and Bakac will determine the rates and pathways by which oxygen is exchanged between various atoms, and they will relate these studies to the current theory which describes electron transfer reactions. They will explore oxygen transfer systems with industrial and biological relevance.

爱荷华州立大学化学系的詹姆斯·埃斯佩森（James Espenson）博士和安德烈贾·巴卡克（Andreja Bakac）博士得到了化学研究部的无机，生物促和有机金属计划的支持，用于开发对氧原子转移的分子水平的理解。他们将探测过渡金属氧和氧复合物的氧原子转移反应的机制。研究包括使用复合物，二氧化亚甲基甲基二氧化甲基甲基甲基原子（MDO）作为原型氧原子受体，无机氧和过渡金属氧络合物作为氧供体。 动力学和热力学测定将根据MARCUS方程构建氧原子转移反应率的尺度。将使用氘同位素效应研究氢键对超氧络合物稳定性的影响，并将研究生物学相关的铬复合物的超氧和氧化物的化学。 将氧原子从一种金属转移到另一种或从金属转移到非金属的化学反应是许多生物学和工业过程的基础。 但是，目前缺乏对这些过程的基本了解，目前阻碍了这一领域的进步。 在这个项目中，Espenson和Bakac将确定各种原子之间氧气交换的速率和途径，它们将将这些研究与描述电子转移反应的当前理论联系起来。 他们将探索具有工业和生物学相关性的氧气转移系统。