CAS: Elucidating Trends in Earth-Abundant Metal Catalyzed Dehydrocoupling

CAS：阐明地球储量丰富的金属催化脱氢偶联的趋势

• 批准号: 2154359
• 负责人: Ryan Trovitch
• 金额: $ 48万
• 依托单位: Arizona State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-06-01 至 2025-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154359&HistoricalAwards=false
• 关键词: CAS; Elucidating; Trends; Earth; Abundant

With the support of the Chemical Catalysis program in the Division of Chemistry, Ryan J. Trovitch of Arizona State University is studying the development of sustainable catalysts that feature abundant, inexpensive metals that do not have known toxicity to the environment. These catalysts will be deployed to synthesize value-added chemicals and polymers in a more efficient manner. This project aims to establish trends that relate to optimal catalyst structure. This information will be used to guide the development of catalysts based on abundant metals for a variety of chemical transformations. The initial reactions of interest will target molecular precursors critical to semiconductor manufacturing. This approach will then be expanded to explore the preparation of anti-corrosion and anti-graffiti coatings for the construction and transportation sectors, compounds for chemical vapor deposition, quantum dot precursors, and reagents for organic synthesis. The broader impacts of this project include the planned development of research-driven undergraduate laboratory experiment(s) and the creation of a manual for sustainable general and inorganic chemistry.With the support of the Chemical Catalysis program in the Division of Chemistry, Ryan J. Trovitch of Arizona State University is studying the development of highly-active manganese, iron, cobalt, and nickel catalysts for the dehydrocoupling of main group hydrides. Physical inorganic techniques will be relied on to elucidate trends in electron count, metal oxidation state, geometry, chelate coordination, and ligand redox activity that correlate with catalyst efficiency and lifetime. This effort will begin with the preparation of arene diimine compounds that are structurally related, yet electronically distinct from popular pyridine diimine compounds. As isostructural series and isoelectronic pairs are characterized, their ability to mediate the dehydrocoupling of amines and silanes will be evaluated. The most effective catalysts will be then used to prepare industrially-relevant aminosilane monomers and polymers. Catalysts developed during this project will also be screened for main group element dehydrocoupling reactions that have not been previously achieved. Applications will include the preparation of chemical vapor deposition and atomic layer deposition precursors that feature N-Ge, N-Al, and Ga-P bonds, quantum dot synthons that feature P-Si and P-Ge bonds, and reductive functionalization reagents that feature B-Si and Al-Si bonds. Overall, this project has the potential to expand the known scope of main-group element dehydrocoupling chemistry and elucidate halogen-free synthetic pathways that can be used to prepare a versatile set of products. The broader impacts of this project include the potential for positive societal outcomes in the fabrication of quantum dots and the distribution of effective catalysts to members of the synthetic community. A sustainable general and inorganic chemistry laboratory guide for post-secondary educators will be developed and undergraduate students will evaluate the sustainability of competing synthetic transformations through the newly developed coursework.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.

在化学系化学催化项目的支持下，亚利桑那州立大学的Ryan J. Trovitch正在研究可持续催化剂的开发，这些催化剂具有丰富，廉价的金属，对环境没有已知的毒性。这些催化剂将用于以更有效的方式合成增值化学品和聚合物。该项目旨在确定与最佳催化剂结构相关的趋势。这些信息将用于指导基于丰富金属的催化剂的开发，用于各种化学转化。感兴趣的初始反应将靶向对半导体制造至关重要的分子前体。然后，这种方法将扩展到探索用于建筑和运输部门的防腐蚀和防涂鸦涂料，化学气相沉积化合物，量子点前体和有机合成试剂的制备。该项目的更广泛的影响包括计划开发研究驱动的本科实验室实验和创建可持续的一般和无机化学手册。在化学系化学催化计划的支持下，亚利桑那州立大学的Ryan J. Trovitch正在研究高活性锰，铁，钴，和镍催化剂，用于主族NH 4的脱氢偶联。物理无机技术将依赖于阐明与催化剂效率和寿命相关的电子计数，金属氧化态，几何形状，螯合配位和配体氧化还原活性的趋势。这一努力将开始与芳烃二亚胺化合物的结构相关，但电子不同于流行的吡啶二亚胺化合物的制备。由于同构系列和等电子对的特点，他们的能力，介导的胺和硅烷的脱氢偶联将进行评估。最有效的催化剂将用于制备工业相关的氨基硅烷单体和聚合物。在本项目期间开发的催化剂也将被筛选用于以前没有实现的主族元素脱氢偶联反应。应用将包括制备化学气相沉积和原子层沉积前体，其特征在于N-Ge，N-Al和Ga-P键，量子点纳米粒子，其特征在于P-Si和P-Ge键，以及还原功能化试剂，其特征在于B-Si和Al-Si键。总的来说，该项目有可能扩大主族元素脱氢偶联化学的已知范围，并阐明可用于制备多功能产品的无卤素合成途径。该项目的更广泛影响包括量子点制造和向合成社区成员分发有效催化剂方面的积极社会成果的潜力。该奖项反映了NSF的法定使命，并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，被认为值得支持。

项目成果

Sustainable preparation of aminosilane monomers, oligomers, and polymers through Si–N dehydrocoupling catalysis

通过 Si−N 脱氢偶联催化可持续制备氨基硅烷单体、低聚物和聚合物

• DOI: 10.1039/d2cc07092h
• 发表时间: 2023
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Leland, Brock E.;Mondal, Joydeb;Trovitch, Ryan J.
• 通讯作者: Trovitch, Ryan J.

Synthesis of Aminosilane Chemical Vapor Deposition Precursors and Polycarbosilazanes through Manganese-Catalyzed Si–N Dehydrocoupling

锰催化硅氮脱氢偶联合成氨基硅烷化学气相沉积前体和聚碳硅氮烷

• DOI: 10.1021/acssuschemeng.2c00008
• 发表时间: 2022
• 期刊: ACS Sustainable Chemistry & Engineering
• 影响因子: 8.4
• 作者: Nguyen, Thao T.;Mukhopadhyay, Tufan K.;MacMillan, Samantha N.;Janicke, Michael T.;Trovitch, Ryan J.
• 通讯作者: Trovitch, Ryan J.

An aryl diimine cobalt( i ) catalyst for carbonyl hydrosilylation

用于羰基硅氢加成的芳基二亚胺钴(i)催化剂

• DOI: 10.1039/d2cc04089a
• 发表时间: 2022
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Sharma, Anuja;So, Sangho;Kim, Jun-Hyeong;MacMillan, Samantha N.;Baik, Mu-Hyun;Trovitch, Ryan J.
• 通讯作者: Trovitch, Ryan J.