Investigations of Metal-Element Multiple Bonding and New Methods for Metal-Mediated Bond Activations

金属元素多重键合和金属介导的键激活新方法的研究

• 批准号: 0649583
• 负责人: Terry Tilley
• 金额: $ 52.7万
• 依托单位: University of California-Berkeley
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2007
• 资助国家: 美国
• 起止时间: 2007-03-01 至 2010-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0649583&HistoricalAwards=false
• 关键词: Investigations; Metal; Element; Multiple; Bonding

Professor T. Don Tilley, Department of Chemistry, University of California at Berkeley is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division to investigate metal-element multiple bonding and new methods for metal-mediated bond activations. A first goal will be to develop hydrosilation catalysts that form a silene ligand by an alpha-migration of a hydrogen atom from silicon to the metal center. A hydrogen atom remaining on the silicon atom then adds directly to an olefin, in a highly anti-Markovnikov manner. The mechanism of this process will be studied to determine the range of substrates that undergo hydrosilation in this way. Structure-reactivity correlations then will be made for these catalysts. Transformations that take advantage of the silicon to metal hydrogen transfer will be developed. Finally, metal-silylyne complexes will be synthesized and their reaction chemistry investigated. This research aims to establish a better understanding of fundamental reaction steps that occur at transition metal centers. The development of new strategies for chemical conversions is an important activity, given potential applications as diverse as drug development, polymer and materials synthesis, and the large-scale production of value-added chemicals. Hydrosilation reactions are of great importance in organic synthesis, and in polymer and materials chemistry. The development of highly regioselective hydrosilation catalysts is expected to contribute to a broader application of this reaction type. The research will train young scientists and provide them a broad set of technical skills. The PI and students involved in this project will take part in outreach activities to middle and high schools.

加州大学伯克利分校化学系T.Don Tilley教授由化学部无机化学、生物无机化学和金属有机化学项目支持，研究金属-元素多键和金属介导键活化的新方法。第一个目标是开发硅氢化催化剂，通过氢原子从硅到金属中心的阿尔法迁移形成硅烯配体。然后，留在硅原子上的氢原子以高度反马尔科夫尼科夫的方式直接加成烯烃。将研究这一过程的机理，以确定以这种方式进行硅氢化的底物的范围。然后将对这些催化剂进行结构-反应性关联。将开发利用硅到金属氢转移的转变。最后，合成了金属-硅炔配合物，并对其反应化学性质进行了研究。这项研究旨在更好地理解过渡金属中心发生的基本反应步骤。鉴于药物开发、聚合物和材料合成以及增值化学品的大规模生产等潜在应用，制定新的化学转化战略是一项重要的活动。硅氢化反应在有机合成、聚合物化学和材料化学中具有重要意义。高区域选择性硅氢加成催化剂的开发有望促进这一反应类型的更广泛应用。这项研究将培训年轻科学家，并为他们提供广泛的技术技能。参与这个项目的学生和学生将参加初中和高中的外展活动。