Metal Complex Activation of Dioxygen

双氧的金属配合物活化

• 批准号: 8808170
• 负责人: Joan Valentine
• 金额: $ 29.31万
• 依托单位: University of California-Los Angeles
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1988
• 资助国家: 美国
• 起止时间: 1988-07-01 至 1991-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8808170&HistoricalAwards=false
• 关键词: Metal; Complex; Activation; Dioxygen

This project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is in the area of bioinorganic chemistry. The focus of the project is nonbiological metal-containing compounds which mimick the action of monooxygenase enzymes. These enzymes, which catalyze the incorporation of oxygen atoms from dioxygen into organic substrates, contain metal ions at their active sites, principally heme iron, non-heme iron and copper. The mechanisms of the reactions of these enzymes are not understood, and it has not been possible thus far to duplicate their reactivities with nonbiological reagents. In an effort to develop "reaction analogies" to the monooxygenase enzymes, reactions of metalloporphyrin peroxo complexes are being studied to learn more about the role of the O-O bond cleavage step in the heme enzymes. To mimick the action of non-heme enzymes, where much less is known about the environment of the metal at the active site, metal-mediated oxygen atom transfer from the single oxygen atom donor iodosylbenzene to organic substrates is under investigation. Also under study are iron-mediated oxygenation reactions using reagents containing intact O-O bonds, i.e. dioxygen, superoxide and peroxide. The results of this research will provide information useful in assessing mechanisms of dioxygen activation in biological systems and in designing catalysts for oxygenation reactions for use in the laboratory and in industrial applications.

该项目在无机，生物无机和有机 化学课程是在生物无机化学领域。的 该项目的重点是非生物含金属 模拟单加氧酶作用的化合物。 这些酶催化氧原子的结合 从分子氧进入有机基质，含有金属离子， 它们的活性部位，主要是血红素铁、非血红素铁和 铜这些酶的反应机制是 不理解，迄今为止还不可能 用非生物试剂复制它们的反应性。中 努力开发单加氧酶的“反应类似物” 酶，金属卟啉过氧络合物的反应， 为了更好地了解O-O键的作用 血红素酶的裂解步骤。模仿的动作 非血红素酶，其中对血红素的了解要少得多。 活性位点处的金属环境，金属介导的 单氧原子供体氧原子转移 碘酰苯对有机底物的影响正在研究中。 还在研究中的是铁介导的氧化反应， 含完整O-O键的试剂，即分子氧、超氧化物 和过氧化物。 这项研究的结果将提供有用的信息， 评估生物学中的分子氧活化机制 系统和设计用于氧化反应的催化剂 用于实验室和工业应用。