Organoboron Derivatives of Group 4 Metals

第 4 族金属的有机硼衍生物

• 批准号: 0108969
• 负责人: Arthur Ashe
• 金额: $ 35.5万
• 依托单位: Regents of the University of Michigan - Ann Arbor
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-08-01 至 2006-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0108969&HistoricalAwards=false
• 关键词: Organoboron; Derivatives; Group; Metals

Dr. Arthur J. Ashe, III, Department of Chemistry, University of Michigan, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for the study of heteroaromatic compounds involving group 13 and 15 elements, their use as ligands to form zirconium complexes, and the development of these complexes as olefin polymerization catalysts. Previous research has demonstrated that boratabenzene zirconium complexes can serve as homogeneous catalysts for the polymerization of olefins. Building on this result and by analogy to ansametallocenes that are known to be active catalysts, a series of metal complexes containing heteroaromatic ligands will be designed with the goal of obtaining highly active and stereospecific olefin polymerization catalysts. Specifically, new oxaborolides, thiaborolides and azaborolides will be synthesized. These compounds along with boratabenzenes, which are bridged through boron or carbon-(2), will be used as ligands to form Group 4 metal complexes, which will be evaluated as polymerization catalysts. Additionally, the conversion of aminoboranediyl bridged zirconocenes to highly active and stereoselective Ziegler-Natta catalysts will be studied.Transition metal complexes promote very selective catalytic and stoichiometric transformations of organic compounds. Much of the unique reactivity at the metal center is a reflection of the density of electrons surrounding the metal and this electron density can be controlled by adjusting the groups that are attached to the metal. A very common 'group' contains a ring of carbon-hydrogen units in what is called an 'aromatic' arrangement. In this project a series of metal complexes will be prepared in which an 'aromatic' group composed of carbon-hydrogen and boron species is attached to a metal. This will permit the electron density about the metal to be carefully adjusted in order to promote specific chemical and catalytic behavior and will set the ground work both to understand existing processes and to rationally design new catalysts.

密歇根大学化学系的亚瑟J.阿什博士III得到化学系无机、生物无机和有机化合物项目的支持，研究涉及第13族和第15族元素的杂芳族化合物，将其用作形成锆络合物的配体，并开发这些络合物作为烯烃聚合催化剂。以往的研究表明硼杂苯锆配合物可以作为烯烃聚合的均相催化剂。基于这一结果并通过类比已知为活性催化剂的安莎金属茂，将设计一系列含有杂芳族配体的金属络合物，目的是获得高活性和立体定向的烯烃聚合催化剂。具体而言，将合成新的氧杂硼杂环戊烯、硫杂硼杂环戊烯和氮杂硼杂环戊烯。这些化合物沿着硼杂苯（其通过硼或碳-（2）桥接）将用作配体以形成第4族金属络合物，其将被评价为聚合催化剂。此外，将研究氨基硼二基桥联的二茂锆转化为高活性和立体选择性的齐格勒-纳塔催化剂。过渡金属配合物促进有机化合物的非常选择性的催化和化学计量转化。金属中心的许多独特反应性是金属周围电子密度的反映，并且可以通过调节连接到金属上的基团来控制这种电子密度。一个非常常见的“基团”包含一个碳-氢单元环，称为“芳香族”排列。在这个项目中，将制备一系列金属络合物，其中由碳-氢和硼物种组成的“芳香族”基团连接到金属上。这将允许仔细调整金属周围的电子密度，以促进特定的化学和催化行为，并为理解现有工艺和合理设计新催化剂奠定基础。