RUI: CAS: Diphosphite Scaffolds for the Synthesis of Bimetallic Complexes Containing Earth Abundant Metals and Strained Rings

在这个项目中，在国家科学基金会化学部化学合成(SYN)计划的支持下，巴克内尔大学的罗伯特·斯托克兰教授正在测试制备含铁、钴和镍的化合物的新方法。最终，这些化合物可能被开发成催化剂，用于加速化学反应，并经常比其他化合物选择性地产生特定的所需产品。该项目旨在利用这些丰富的金属最终取代稀有金属和贵金属。主要的挑战是提高丰富的金属化合物的性能，使其与稀有金属的性能相匹配。为此，斯托克兰德教授正在检验一种假设，即成对的丰富金属将显示出增强的性质。他正在设计稳定这些金属对的有机化合物。这项研究为本科生研究人员提供了实践培训。他们的实验室培训需要有处理许多不同类型的化合物、用于化学合成的仪器和用于表征新材料的工具的经验。这项研究有望提高参与学生的留存率和成功率，并为他们的技术职业生涯做好准备。利用富含稀土的金属(如铁、钴或镍)作为试剂或催化剂的化学转化的发展是目前合成界感兴趣的一个领域。虽然许多配体骨架结合多个金属中心并促进协同作用，但很少有已知的配体能最小化协同活性并促进协同作用。在这个项目中，在化学系化学合成(SYN)计划的支持下，巴克内尔大学的罗伯特·斯托克兰教授和他的学生正在使用刚性螺环二亚磷酸通过原脱金属、转金属和碱助膦酰化制备双金属化合物。此外，选择性地用一种金属取代另一种金属可得到异双金属化合物。在这些结果的基础上，通过交叉偶联化学将氧、磷和硫供体并入母体二亚磷酸酯核心。这些官能化的二亚磷酸盐为结合EAMS提供了独特的结构。此外，二亚磷酸盐是构建一系列含有共轭片段的环状磷酸盐的入口点。炔烃和官能化的芳基组成环状膦酸酯的不饱和成分。本科生的研究往往是激发学生好奇心、促进科学、技术、数学和工程职业发展的关键经历。巴克内尔大学斯托克兰组的学生正在获得实践经验，并为进入化学专业或研究生课程做好了准备。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, with support from the Chemical Synthesis (SYN) Program in the Division of Chemistry of the National Science Foundation, Professor Robert Stockland of Bucknell University is testing new approaches for the preparation of chemical compounds containing iron, cobalt, and nickel. Ultimately, these compounds may be developed into catalysts that are used to speed up chemical reactions and often to selectively produce specifically desired products over others. The project aims to use these abundant metals to ultimately replace rare and precious metals. The main challenge is to enhance the properties of abundant metal-based compounds to match those of the rarer metals. To this end, Professor Stockland is examining the hypothesis that pairs of abundant metals will exhibit enhanced properties. He is designing organic compounds that stabilize such pairs of metals. The research provides undergraduate researchers with hands-on training. Their laboratory training entails experience the handling many different kinds of chemical compounds, the apparatus used for chemical synthesis, and the tools used to characterize the new materials. This research is expected to improve the retention and success rates of the participating students and prepare them for technical careers. The development of chemical transformations that employ earth abundant metals (EAMs) such as iron, cobalt, or nickel as reagents or catalysts is an area of current interest in the synthetic community. While a number of ligand frameworks bind multiple metal centers and promote cooperative interactions, few ligands are known to minimize cooperative activity and promote synergistic interactions. In this project, with support from the Chemical Synthesis (SYN) Program in the Division of Chemistry, Professor Robert Stockland of Bucknell University and his students are using rigid spirocyclic diphosphites to prepare bimetallic compounds through protodemetalation, transmetalation, and base assisted phosphonylation. Furthermore, the selective substitution of one metal for another affords heterobimetallic compounds. Building on these results, the incorporation of oxygen, phosphorus, and sulfur donors into the parent diphosphite core is accomplished through cross-coupling chemistry. These functionalized diphosphites provide unique architectures for binding EAMs. Additionally, the diphosphites are entry points for the construction of a series of cyclic phosphonates containing conjugated fragments. Alkynes and functionalized aryl groups comprise the unsaturated components of the cyclic phosphonates. Undergraduate research is often a pivotal experience that stimulates student curiosity and promoted careers in science, technology, math and engineering. Students in the Stockland group at Bucknell University are gaining hands-on experience and are well prepared to enter the chemical profession or graduate programs.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.