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

LEAPS-MPS 发现地球丰富的过渡金属催化剂，用于小分子功能化和机理见解

• 批准号: 2316526
• 负责人: REBECA AREVALO
• 金额: $ 25万
• 依托单位: University of California - Merced
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-09-01 至 2025-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2316526&HistoricalAwards=false
• 关键词: LEAPS; MPS; Discovery; Earth; abundant

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.

在NSF化学部门管理的该项目中，丽贝卡·阿雷瓦洛（Rebeca Arevalo）教授及其学生在加利福尼亚大学（University of California of California）进行的研究将进行研究，旨在通过地球丰富的金属络合物探索新的债券激活策略，并将这种知识利用这种知识，以发现可持续的催化剂，以使小分子的惰性粘合物功能化。特别是，将针对不同类型的C-H键，这是有机分子中最强的，并且需要珍贵金属，其裂解具有有限的地球丰度。 Arevalo教授和她的学生将以可持续性和绿色的金属为目标，以实现C-H键功能化，并将挖掘综合体的设计要求，以提高效率。他们将研究新复合物与硅和含磷的供体的合成，表征和催化反应。他们的研究可以为催化剂设计提供有价值的见解，以构成功能分子的合成。该项目将提供代表性不足的西班牙裔学生，为空气和水分敏感的金属络合物的合成和表征以及催化中的机理研究知识提供了经验，并构成了UC Merced的教学材料和新课程的起点。 Arevalo教授和她的学生将综合新的地球量过渡金属复合物，并评估其作为均质催化剂的效率，用于惰性C（SP3）-H键的功能化以及涉及C（SP）-H功能化的串联过程。将重点放在第一行过渡金属配合物上，其中将探索两种不同的策略以进行键激活（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键的功能化将通过涉及可持续催化剂和原料起始材料的新合成途径来访问药物行业和材料化学的有价值的合成，这些途径由于其惰性而可能不适合。 Arevalo教授及其学生将旨在通过机械研究和合理的催化剂设计来阐明催化剂设计有效化催化剂的钥匙。他们的结果将有助于增加对未倍增的地球过渡金属有机金属化学的知识，并开放新的途径，以发现有机分子中强键的新策略。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法来表征催化剂和新功能分子，并在催化中对操作的周期进行见解。该奖项反映了NSF的法定任务，并通过评估了范围的范围，并通过评估了范围的范围。