CAREER: Advancing Light-mediated Ni Catalysis using Data Science and Physical Organic Techniques

在化学部化学催化项目的资助下，加州大学河滨分校的Bahamonde博士将研究镍/光氧化还原催化。使用基于Pd、Rh、Ir和Ru的过渡金属催化剂的稀缺性和高昂的成本激发了人们对利用富含稀土的过渡金属的互补催化过程的浓厚兴趣。其中，镍配合物独特的单电子化学反应和光化学反应使上述金属基本上无法实现的新的反应模式成为可能。为了在工业环境中实施这些新技术，进一步提高催化剂的性能和选择性是至关重要的。然而，目前，科学家们并不完全了解如何控制这些反应，以选择性地产生目标分子，而不是竞争对手的副产品。在这个项目中，Bahamonde博士的目标是更深入地了解是哪些镍催化剂的特性推动了这些反应，并利用这些信息来开发更具选择性的新催化剂。Bahamonde博士将积极参与以她的研究为基础的外展活动，以促进学生对科学、技术、工程和数学(STEM)学科的参与。这些活动包括在Bahamonde博士的实验室进行暑期研究实习，以及在当地社区大学举办网络活动，旨在激发高中和社区大学学生追求高等教育和STEM职业的兴趣。该项目的研究将集中在镍/光氧化还原催化，特别强调了解有利于选择性形成新的C-C和C-N键的配体特征。手性镍配合物将被用来探索对映体选择性的酰胺和C(SP3)-H的官能化，以获得氮、α-杂原子和远程官能化。为了加快反应优化，将观察到的对映体选择性关联到计算分子描述符的多元线性回归模型将被开发出来。了解什么配基特征可以促进选择性地访问这些可选流形中的任何一个也将被调查。Bahamonde博士将参与旨在缩小STEM研究中的性别差距、将社区大学生转移到四年制大学和高中生研究实习的外联计划。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 funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Bahamonde of the University of California-Riverside will study Ni/photoredox catalysis. The scarcity and high cost of using transition metal catalysts based on Pd, Rh, Ir, and Ru has spurred intense interest in the development of complementary catalytic processes employing earth-abundant transition metals. Among these, the distinct one-electron chemistry and photochemical reactivity of Ni complexes has enabled new modes of reactivity that are largely inaccessible to the aforementioned metals. For the implementation of these new technologies in industrial settings, it is critical to further increase catalyst performance and selectivity. However, currently, scientists do not completely understand how these reactions can be controlled to selectively produce the target molecule over competing byproducts. In this project, Dr. Bahamonde aims to gain a deeper understanding of what Ni-catalyst features drive these reactions and use this information to develop new catalysts that are more selective. Dr. Bahamonde will actively engage in outreach activities that build upon her research to promote engagement of students in science, technology, engineering, and mathematics (STEM) disciplines. These activities, which include summer research internships in Dr. Bahamonde’s laboratory and networking events at local community colleges, will be directed at stimulating the interest of high school and community college students to pursue higher education and STEM careers. Research in this project will be focused on Ni/photoredox catalysis with a special emphasis on understanding the ligand features that favor the selective formation of new C–C and C–N bonds. Chiral Ni complexes will be utilized to explore enantioselective amide and C(sp3)–H functionalization in order to access nitrogen, alpha-heteroatom, and remote functionalizations. To expedite reaction optimization, multivariate linear regression models correlating observed enantioselectivity to compute molecular descriptors will be developed. Understanding what ligand characteristics can facilitate selective access to either of these alternative manifolds will be investigated as well. Dr. Bahamonde will engage in outreach programs focused on narrowing the gender gap in STEM research, the transfer of community college students to 4-year universities, and high school student research internships.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.