Synthesis and Chemistry of Carboxylate-Bridged Polymetallic Complexes

羧酸桥多金属配合物的合成与化学

• 批准号: 9727243
• 负责人: Stephen Lippard
• 金额: --
• 依托单位: Massachusetts Institute of Technology
• 依托单位国家: 美国
• 项目类别: Continuing grant
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-02-01 至 2003-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9727243&HistoricalAwards=false
• 关键词: Synthesis; Chemistry; Carboxylate; Bridged; Polymetallic

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program provides continued support for research on carboxylate-bridged metal dimers by Dr. Stephen J. Lippard, Chemistry Department, Massachusetts Institute of Technology. Metalloproteins containing such units are responsible for many biological functions, including oxygen transport, methane hydroxylation, and hydrolysis of phosphate esters. In this study, three lines of investigation will be pursued: oxidation chemistry of diiron complexes as models for the active site of the hydroxylase component of methane monooxygenase; metallohydrolase chemistry that mimics urease and metalophosphatase; and sugar isomerization reactions to model D-xylose isomerase. Emphasis will be placed on designing dinucleating ligands that have sufficient internal preorganization so that they fold into shapes that create the appropriate cavities for metal binding. One class of ligands is dicarboxylates in which two Kemp's triacid anhydride-chloride moities are linked by a bridging 1,3-diaminoxylene, 1,4-diaminophthalazine, or bis(aminomethylphenyl)porphyrin group. Symmetric and unsymmetrically substituted amidinate ligands, that are isoelectronic with carboxylate, will also be investigated. Attempts will also be made to functionalize mono-carboxylate bridged systems using a multicomponent ligand with two terminal bidentate units joined by one bridging carboxylate spacer. The compounds synthesized will be tested to see the extent to which they mimic the structures, physical properties, and reactivities of the biological prototypes, including intermediates in catalytic cycles. Many biologically-important hydroxylases, hydrolases, and isomerases function because of a reaction center that contains two linked metal atoms and a surrounding carboxylate group. In order to understand the details of how these enzymes work, model compounds will be designed, synthesized, and tested for catalytic activity.

该奖项在无机，生物无机和有机化学 该计划为羧酸盐桥接的研究提供持续支持 金属二聚体，化学系Stephen J. Lippard博士， 马萨诸塞州理工学院。 含有这种金属蛋白的 单位负责许多生物功能，包括氧气 运输、甲烷羟基化和磷酸酯水解。 在 本研究将进行三方面的研究： 作为活性位点模型的二铁配合物化学 甲烷单加氧酶羟化酶组分;金属水解酶 化学模拟尿素酶和金属磷酸酶;和糖 异构化反应以模拟D-木糖异构酶。 重点将 放在设计双核配体，具有足够的内部 预组织，使它们折叠成形状， 用于金属粘合的空腔。 一类配体是二羧酸酯， 其中两个肯普三酸酐-氯化物部分通过 桥连1，3-二氨基二甲苯、1，4-二氨基酞嗪，或 双（氨甲基苯基）卟啉基团。 对称与非对称 取代的脒基配体，其与羧酸根等电子， 也将受到调查。 还将尝试将功能化 使用多组分配体的单羧酸盐桥接体系， 末端双齿单元通过一个桥接羧酸酯间隔基连接。 的 合成的化合物将被测试，看看它们在多大程度上， 模拟的结构，物理性质，和反应性的 生物原型，包括催化循环中的中间体。 许多生物重要的羟化酶、水解酶和异构酶 因为反应中心含有两个连接的金属， 原子和周围的羧酸根基团。 为了解 这些酶如何工作的细节，模型化合物将被设计， 合成并测试催化活性。