Transition Metal - Main Group Multiple Bonding

过渡金属 - 主族多重键合

• 批准号: 2349123
• 负责人: Terry Tilley
• 金额: $ 59万
• 依托单位: University of California-Berkeley
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2024
• 资助国家: 美国
• 起止时间: 2024-04-01 至 2027-03-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2349123&HistoricalAwards=false
• 关键词: Transition; Metal; Main; Group; Multiple

With the support of the Chemical Synthesis (SYN) program in the Division of Chemistry, Professor T. Don Tilley of the University of California, Berkeley will study new structures and reactions of chemical compounds that incorporate both a transition metal and silicon. Discoveries in this area are expected to provide new compounds and chemical transformations that accelerate emerging applications of silicon-based materials, which include silicone polymers, adhesives, lubricants, and semiconductors. A primary objective is the study of a little understood type of chemical compound that features silicon atoms bonded only to metal centers. Such compounds are expected to exhibit properties that have yet to be thoroughly explored, but promise to aid the improvement of industrial processes. In addition, this program prepares graduate and undergraduate students for careers in science by providing a research environment that fosters critical thinking and problem-solving skill development. There is an important educational-outreach component that include work with transfer students to ease their entry into the Berkeley program. Students will participate in outreach programs that include hosting high school students and engaging with local elementary schools to teach basic scientific principles through interactive lessons. There is a long standing strong record of training of research students; this training includes preparing students to work with challenging chemicals and reagents.Complexes that formally possess a multiple bond between a metal and silicon, such as silylene complexes (LnM=SiRR'), have attracted considerable interest over the years, for their assumed or established role in catalytic processes such as silylene-transfer or hydrosilylation. The focus of this project will center on development of a better understanding of chemical properties associated with multiple bonding, with three primary aims designed to (1) expand the knowledge base for metal silylene complexes formally possessing M=Si double bonds, (2) explore a new class of compounds – molecular silicide complexes with M=Si=M cores, and (3) develop informative, periodic relationships to metal-element multiple bonds involving the heavier group 14 elements germanium, tin, and lead. A central objective will be establishing principles that govern formation and transformations of the molecular silicides, containing metal-ligated silicon atoms. For comparison, solid-state metal silicides are of immense technological importance as catalysts that make and break bonds to silicon, as in the direct process for the synthesis of organosilanes from elemental silicon. Despite the technological importance of transition-metal silicides, little is known about their reaction mechanisms and this knowledge gap makes it difficult to design processes that utilize silicides as synthetic intermediates. Molecular silicides should be amenable to mechanistic investigation and development of homogeneous transformations of silicon compounds.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系化学合成（SYN）项目的支持下，加州大学伯克利分校的 T. Don Tilley 教授将研究包含过渡金属和硅的化合物的新结构和反应。该领域预计将提供新的化合物和化学转化，以加速硅基材料的新兴应用，其中包括有机硅聚合物、粘合剂、润滑剂和半导体。主要目标是研究一种鲜为人知的以硅原子为特征的化合物。保税的此类化合物预计将表现出尚未被彻底探索的特性，但有望帮助改进工业流程。此外，该项目通过提供一个研究环境为研究生和本科生从事科学职业做好准备。培养批判性思维和解决问题的技能发展。有一个重要的教育外展部分，包括与转学生合作，以方便他们进入伯克利项目。学生将参加外展项目，包括接待高中生和与当地小学互动。学校通过互动课程教授基本科学原理由来已久。良好的研究生培训记录；这种培训包括让学生做好使用具有挑战性的化学品和试剂的准备。在金属和硅之间正式具有多重键的络合物，例如亚硅基络合物（LnM=SiRR'），引起了人们的极大兴趣多年来，他们在催化过程（如硅基转移或氢化硅烷化）中假定或确立的作用。该项目的重点将集中于更好地理解与多重键相关的化学性质，设计了三个主要目标。 (1) 扩展正式具有 M=Si 双键的金属硅烯配合物的知识库，(2) 探索一类新的化合物 - 具有 M=Si=M 核的分子硅化物配合物，以及 (3) 开发信息丰富的周期性关系与金属元素多重键相比，较重的 14 族元素（包括锗、锡和铅）的中心目标是建立控制分子硅化物（包含金属配位硅原子）的形成和转变的原理。固态金属硅化物作为硅的形成和键断裂催化剂具有巨大的技术重要性，例如在从元素硅合成有机硅烷的直接过程中，尽管过渡金属硅化物具有重要的技术重要性，但人们对它们的反应知之甚少。机制和这种知识差距使得设计利用硅化物作为合成中间体的工艺变得困难。分子硅化物应该适合硅化合物均相转变的机理研究和开发。该奖项反映了这一点。通过使用基金会的智力价值和更广泛的影响审查标准进行评估，NSF 的法定使命被认为值得支持。