LEAPS-MPS Discovery of Earth-abundant Transition-metal Catalysts for Small Molecule Functionalization and Mechanistic Insights

在这个由NSF化学部管理的项目中，加州大学默塞德分校的Rebeca Arevalo教授和她的学生将进行研究，旨在探索地球上丰富的金属络合物激活键的新策略，并利用这些知识发现可持续的催化剂，用于小分子中惰性键的功能化。特别是，不同类型的C-H键将成为目标，这些键是有机分子中最强的键之一，需要地球丰度有限的贵金属才能裂解。Arevalo教授和她的学生将以可持续和绿色的金属为目标，实现C-H键的功能化，并将深入研究高效的络合物的设计要求。他们将研究与硅和含磷供体的新络合物的合成、表征和催化反应。他们的研究可以为合成功能分子的催化剂设计提供有价值的见解。该项目将为人数不足的拉美裔学生提供空气和湿度敏感金属络合物的合成和表征方面的经验，以及催化方面的机械研究知识，并成为加州大学默塞德分校教学材料和新课程创建的起点。Arevalo教授和她的学生将合成新的富含地球的过渡金属配合物，并评估它们作为惰性C(Sp3)-H键功能化和涉及C(Sp)-H官能化的串联过程的均相催化剂的效率。重点将放在第一排过渡金属络合物上，在那里将探索两种不同的键激活策略：(A)以金属为中心的过程和(B)金属-配体合作。惰性小分子中C-H键的功能化将使人们能够通过新的合成路线获得对制药工业和材料化学有价值的合成物，这些合成路线涉及可持续的催化剂和原料，这些原料可能因其惰性而被认为不适合使用。Arevalo教授和她的学生将致力于通过机理研究和合理的催化剂设计来阐明设计高效C-H官能化催化剂的关键。他们的结果将有助于增加对未被探索的地球丰富的过渡金属有机金属化学的了解，并为发现激活有机分子中强键的新策略开辟新的途径。他们将使用核磁共振、电子顺磁共振和红外光谱以及单晶X射线衍射和气相色谱来表征催化剂和新的功能分子，并深入了解催化剂中运行的循环。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。

In this project managed by the Chemistry Division at NSF, Professor Rebeca Arevalo and her students at the University of California, Merced will perform studies that aim to explore new bond-activation strategies by Earth-abundant metal complexes and leverage this knowledge to the discovery of sustainable catalysts for the functionalization of inert bonds in small molecules. In particular, different types of C-H bonds will be targeted, which are amongst the strongest in organic molecules and require precious metals with limited Earth-abundance for its cleavage. Professor Arevalo and her students will target sustainable and green metals to achieve C-H bond functionalization and will dig into the design requirements of the complexes to be efficient. They will investigate the synthesis, characterization, and catalytic reactions of new complexes with silicon and phosphorous-containing donors. Their studies could provide valuable insights for catalyst design for the synthesis of functional molecules. This project will serve to provide underrepresented Hispanic students with experience in synthesis and characterization of air- and moisture-sensitive metal complexes and with knowledge in mechanistic studies in catalysis, as well as constitute a starting point for the creation of instructional materials and new curriculum at UC Merced. Professor Arevalo and her students will synthesize new Earth-abundant transition-metal complexes and evaluate their efficiency as homogeneous catalysts for the functionalization of inert C(sp3)-H bonds and for tandem processes involving C(sp)-H functionalization. The focus will be placed on 1st-row transition-metal complexes where two different strategies will be explored for bond activation (a) metal-centered processes and (b) metal-ligand cooperation. The functionalization of C-H bonds in inert small molecules will render access to valuable synthons for pharma industry and materials chemistry by new synthetic routes involving sustainable catalysts and feedstock starting materials that might be considered as unsuitable due to their inertness. Professor Arevalo and her students will aim to elucidate the keys for the design of catalysts efficient for C-H functionalization through mechanistic studies and rational catalyst design. Their results will contribute to increase the knowledge of the underexplored Earth-abundant transition-metal organometallic chemistry and open new avenues for the discovery of new strategies for the activation of strong bonds in organic molecules. They will use NMR, EPR and IR spectroscopy as well as single-crystal X-ray diffraction and gas chromatography to characterize the catalysts and the new functional molecules and gain insights into the cycles operative in catalysis.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.