CAS: Elucidating Trends in Earth-Abundant Metal Catalyzed Dehydrocoupling

在化学系化学催化项目的支持下，亚利桑那州立大学的瑞安·J·特罗维奇正在研究可持续催化剂的开发，这种催化剂具有丰富、廉价的金属，对环境没有已知的毒性。这些催化剂将被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。这些信息将被用来指导基于丰富金属的催化剂的开发，用于各种化学转化。令人感兴趣的最初反应将针对对半导体制造至关重要的分子前体。这一方法将被扩展到建筑和运输领域的防腐和防涂鸦涂层的制备、化学气相沉积的化合物、量子点前体和有机合成试剂的制备。这个项目的更广泛的影响包括计划开发以研究为导向的本科实验室实验(S)和创建可持续通用和无机化学手册。在化学系化学催化项目的支持下，亚利桑那州立大学的莱恩·J·特罗维奇正在研究用于主族氢化物脱氢偶联的高活性锰、铁、钴和镍催化剂的开发。将依靠物理无机技术来阐明与催化剂效率和寿命相关的电子计数、金属氧化态、几何构型、络合配位和配体氧化还原活性的趋势。这项工作将从制备芳香族二亚胺化合物开始，这些化合物在结构上相关，但在电子上与流行的吡啶二亚胺化合物不同。随着等结构系列和等电子对的表征，它们介导胺和硅烷脱氢偶联的能力将被评估。然后，最有效的催化剂将被用于制备与工业相关的氨基硅烷单体和聚合物。在该项目期间开发的催化剂还将用于以前尚未实现的主族元素脱氢偶联反应的筛选。应用将包括制备以N-Ge、N-Al和Ga-P键为特征的化学气相沉积和原子层沉积前体，以P-Si和P-Ge键为特征的量子点合成子，以及以B-Si和Al-Si键为特征的还原功能化试剂。总体而言，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种产品的无卤素合成途径。该项目的更广泛影响包括在制造量子点方面可能产生积极的社会结果，以及向合成社区成员分发有效的催化剂。将为大专教育工作者制定可持续的普通和无机化学实验室指南，本科生将通过新开发的课程评估相互竞争的合成转化的可持续性。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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.