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

在这个由美国国家科学基金会化学部管理的项目中，丽贝卡·阿雷瓦洛教授和她在加州大学默塞德分校的学生将进行研究，旨在探索地球上丰富的金属配合物的新键活化策略，并利用这些知识来发现可持续催化剂，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，需要地球储量有限的贵金属来裂解。 Arevalo 教授和她的学生将瞄准可持续和绿色金属，以实现 C-H 键功能化，并将深入研究配合物的高效设计要求。他们将研究含硅和磷供体的新型配合物的合成、表征和催化反应。他们的研究可以为功能分子合成的催化剂设计提供有价值的见解。该项目将为代表性不足的西班牙裔学生提供对空气和湿度敏感的金属络合物的合成和表征经验以及催化机理研究的知识，并为加州大学默塞德分校创建教学材料和新课程奠定基础。 Arevalo 教授和她的学生将合成新的地球丰富的过渡金属配合物，并评估其作为惰性 C(sp3)-H 键功能化和涉及 C(sp)-H 功能化的串联过程的均相催化剂的效率。重点将放在第一行过渡金属配合物上，其中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键的功能化将为制药工业和材料化学提供有价值的合成子，通过涉及可持续催化剂和原料起始材料的新合成路线，这些原料可能由于其惰性而被认为是不合适的。 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有效 C-H 官能化催化剂设计的关键。他们的研究结果将有助于增加对地球上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途径。他们将使用 NMR、EPR 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功能分子，并深入了解催化中的循环。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值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.