CAREER: Roadmaps for Developing Hypervalent Phosphorus-Based Main Group Catalysts and Bridging Gaps in STEM Education in Hawaii

催化剂是一种加速或促进化学反应的物质。催化剂对化学和制药工业至关重要，它们用于减少化学过程的能量需求和定向精确的化学转化。许多最活跃的催化剂都是基于稀有金属的，这些金属非常昂贵，而且很难找到和分离。当前研究的一个重要领域是寻找这些昂贵催化剂的廉价、丰富的替代品。磷(P)是一种储量丰富、价格低廉的元素。然而，基于它设计催化剂的努力很少。夏威夷大学马诺阿分校化学系的马修·凯恩博士在化学系化学合成项目的支持下，制备了不寻常的化合物，其中磷原子处于不寻常的氧化状态，在某些情况下可能表现得像金属。因此，磷可以替代目前使用的稀有、昂贵的金属催化剂。这项研究可能会产生非常不寻常的催化剂，这可能会产生变革性的影响——在主要的工业和制药反应中取代昂贵且有毒的铂族金属。此外，该项目还包括一个教育部分，旨在吸引夏威夷原住民学生进入科学领域。夏威夷原住民虽然在夏威夷州人口中占相当大的一部分，但在科学技术领域的代表却很少。因此，项目的这一方面为夏威夷原住民提供了一个重要的新机会。利用具有赤道碳芳基给体和吸电子轴向给体的单阴离子螯钳，制备了具有正确前沿轨道环境以促进氧化加成的10-P-3高价物质。对不饱和底物的配位和插入以及10-P-5中心的还原消除的基础研究探讨了关闭潜在催化循环的可行性。最后，用10-P-3催化剂测试了简单有机底物的1,2-二官能化，特别是氢化，氢硅化和二硼化。此外，该项目正在开发一种三层方法，以展示、吸引和激励夏威夷原住民和亚裔美国人/夏威夷出生的人口参与科学、技术、工程和数学。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

A catalyst is a substance that speeds or facilitates a chemical reaction. Catalysts are critical to the chemical and pharmaceutical industries where they are used to reduce energy requirements of chemical processes and to orient precise chemical transformations. Many of the most active catalysts are based on rare metals that are quite costly and difficult to find and isolate. An important area of current research seeks to find cheap, abundant replacements for these expensive catalysts. Phosphorus (P) is an abundant, inexpensive element. However, there has been little effort made to devise catalysts based on it. Dr. Matthew Cain, Department of Chemistry, University of Hawaii at Manoa, is supported by the Chemical Synthesis Program of the Chemistry Division, to prepare unusual compounds where phosphorus atoms are in unusual oxidation states and may behave like metals under certain circumstances. Thus, phosphorus may represent an alternative to the rare, expensive metal catalysts currently being used. This research may lead to highly unusual catalysts which could have transformative impact - replacing expensive and toxic platinum group metals in major industrial and pharmaceutical reactions. In addition, this project includes an educational component that is designed to attract Native Hawaiian students into science. Native Hawaiians, although they constitute a sizable fraction of the population in the State of Hawaii, are very underrepresented in science and technology. Thus, this aspect of the projects provides an important, new opportunity to the Native Hawaiian population. Using monoanionic pincers featuring an equatorial carbon-aryl donor and electron-withdrawing axial donors, hypervalent 10-P-3 species with the correct frontier orbital environment to promote oxidative addition are prepared. Fundamental studies on coordination and insertion of unsaturated substrates and reductive elimination from 10-P-5 centers probe the feasibility of closing a potential catalytic cycle. Ultimately, 1,2-difunctionalization, particularly, hydrogenation, hydrosilation, and diboration of simple organic substrates is tested with 10-P-3 catalysts. In addition, the project is developing a three-tiered approach of exposing, attracting, and inspiring the Native Hawaiian and Asian-American/Hawaiian-born population to become involved in science, technology, engineering, and mathematics.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.