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

T. Don Tilley教授，加州大学伯克利分校化学系，受化学系无机、生物无机和有机金属化学项目的支持，研究金属-元素多重键和金属介导键激活的新方法。第一个目标将是开发氢硅化催化剂，通过氢原子从硅到金属中心的α迁移形成硅烯配体。一个留在硅原子上的氢原子然后以一种高度反马尔可夫尼科夫的方式直接加到烯烃上。这一过程的机制将被研究，以确定底物的范围，以这种方式进行氢硅化。然后将对这些催化剂进行结构-反应性相关性分析。利用硅到金属氢转移的转化将被开发出来。最后，合成了金属-硅烷配合物，并对其反应化学进行了研究。本研究旨在更好地了解发生在过渡金属中心的基本反应步骤。考虑到药物开发、聚合物和材料合成以及增值化学品的大规模生产等多种潜在应用，开发化学转化新战略是一项重要活动。氢硅化反应在有机合成、高分子化学和材料化学中具有重要意义。高区域选择性氢化硅催化剂的开发有望为该反应类型的更广泛应用做出贡献。这项研究将训练年轻科学家，并为他们提供广泛的技术技能。PI和参与该项目的学生将参加到初中和高中的外展活动。

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.