Early Transition Metal Complexes with Polydentate Polyanionic Ligands as Olefin Polymerization Catalysts

早期过渡金属配合物与多齿聚阴离子配体作为烯烃聚合催化剂

• 批准号: 9523279
• 负责人: James Boncella
• 金额: $ 24.4万
• 依托单位: University of Florida
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1995
• 资助国家: 美国
• 起止时间: 1995-12-01 至 1999-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9523279&HistoricalAwards=false
• 关键词: Early; Transition; Metal; Complexes; Polydentate

This project supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program will support the continuation of studies of transition metal polymerization catalysts by Professor J. Boncella of the University of Florida. Studies of transition metal complexes of polydentate, polyanionic ligands will be undertaken with the following objectives: 1) continued development of catalysts for olefin metathesis polymerization and depolymerization with emphasis on the mechanism of action of a recently developed tungsten-based catalyst of N,N'-bis(trimethylsilyl)-o-phenylenediamide, 2) possible applications for C-H bond activation reactions that are observed with this tungsten compound, 3) development of catalysts that will perform both metathesis polymerization and Zeigler-Natta type polymerizations at the same metal center, and 4) the synthesis of a new class of polyanionic ligands based upon the pyrrolide ligand, including some that carry more charge than ligating atoms. This new class of ligands is expected to lead to the synthesis of high oxidation state early transition metal complexes that have unusually low coordination numbers and which may have enhanced reactivity. The properties of transition metal catalysts are critically dependent upon the type and number of groups (ligands) that are attached to the active metal center. This project involves the synthesis and study of several new catalysts. Among objectives of this research are 1) the development of new types of polymerization catalysts that are thermally robust and allow for the polymerization of monomers that cannot currently be polymerized because of catalyst instability, and 2) the development of dual function catalysts that can be used to co-polymerize two monomers that undergo polymerization by different mechanisms.

该项目由无机、生物无机和有机金属化学项目支持，将支持佛罗里达大学 J. Boncella 教授继续进行过渡金属聚合催化剂的研究。 对多齿、多阴离子配体的过渡金属配合物的研究将实现以下目标：1）继续开发用于烯烃复分解聚合和解聚的催化剂，重点是最近开发的N,N'-双（三甲基甲硅烷基）-邻苯二酰胺钨基催化剂的作用机制，2）C-H键活化的可能应用 使用这种钨化合物观察到的反应，3）开发可在同一金属中心进行复分解聚合和齐格勒-纳塔型聚合的催化剂，以及4）基于吡咯烷配体合成一类新型聚阴离子配体，包括一些比配位原子携带更多电荷的配体。 这类新型配体预计将导致高氧化态早期过渡金属配合物的合成，这些配合物具有异常低的配位数，并且可能具有增强的反应性。 过渡金属催化剂的性能很大程度上取决于连接到活性金属中心的基团（配体）的类型和数量。 该项目涉及几种新型催化剂的合成和研究。 这项研究的目标包括：1）开发新型聚合催化剂，该催化剂具有热稳定性，可以聚合目前由于催化剂不稳定而无法聚合的单体；2）开发双功能催化剂，可用于共聚两种通过不同机制进行聚合的单体。