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

T.教授唐蒂利，化学系，加州大学伯克利分校的支持下，无机，生物无机和有机化学计划的化学部门，研究金属元素的多重键和新的方法，金属介导的键活化。 第一个目标将是开发硅氢化催化剂，其通过氢原子从硅到金属中心的α-迁移形成硅烯配体。留在硅原子上的氢原子然后以高度反马尔可夫尼科夫的方式直接加成到烯烃上。将研究该过程的机制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换。最后，将合成金属-硅炔配合物并研究其反应化学。这项研究旨在更好地了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多种多样的潜在应用，制定化学转化的新战略是一项重要活动。硅氢加成反应在有机合成、高分子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为这类反应的更广泛应用做出贡献。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。参与该项目的PI和学生将参加初中和高中的外联活动。

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.