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行业至关重要，它们用于降低化学过程的能源需求并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，这些金属非常昂贵，难以找到和分离。目前研究的一个重要领域是寻找廉价、充足的替代品来取代这些昂贵的催化剂。磷（P）是一种丰富而廉价的元素。然而，在此基础上设计催化剂的努力很少。夏威夷化学系的Matthew Cain博士在化学部化学合成计划的支持下，制备了磷原子处于不寻常氧化态的不寻常化合物，在某些情况下可能表现得像金属。因此，磷可能是目前使用的稀有、昂贵的金属催化剂的替代品。 这项研究可能会产生非常不寻常的催化剂，这些催化剂可能会产生变革性的影响-取代主要工业和制药反应中昂贵和有毒的铂族金属。 此外，该项目包括一个教育部分，旨在吸引夏威夷土著学生进入科学。夏威夷土著人虽然在夏威夷州人口中占相当大的比例，但在科学和技术领域的代表性非常低。因此，项目的这一方面为夏威夷土著居民提供了一个重要的新机会。使用具有赤道碳芳基供体和吸电子轴向供体的单阴离子钳，制备具有正确前线轨道环境以促进氧化加成的高价10-P-3物种。 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索了关闭潜在催化循环的可行性。最后，1，2-双官能化，特别是，氢化，硅氢化，和简单的有机底物的二硼化测试与10-P-3催化剂。此外，该项目正在开发一种三层方法，以暴露、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。

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.