Nonspectator Phosphorus Ligands for Catalysis

马萨诸塞州化学系的亚历山大·拉多塞维奇在化学系化学催化和化学结构、动力学和机理B计划的支持下，正在研究开发新型金属-磷络合物作为小分子转化化学的均相催化剂。催化在可扩展，经济和可持续的化学品合成中发挥着核心作用，包括燃料，药物和材料。在这个项目中，Radosevich博士和他的学生正在创造新的金属基催化剂，这些催化剂带有以新方式反应的含磷取代基。在这项研究中所追求的具体反应包括将烯烃和醇转化为增值产品的方案。Radosevich博士的研究生和本科生研究人员将接受广泛的光谱，物理和合成化学技术的培训。实现这些培训目标将有助于建立一支重要的劳动力队伍，支撑美国化学工业的经济竞争力。Radosevich博士和他的研究小组参与了一些推广工作，以推动广泛参与科学的目标。Radosevich博士的实验室也接待了来自世界各地的研究人员，为美国在国际科学领域的领导地位做出了贡献。亚历山大和他的研究团队正在为基于三配位磷的新型非旁观者配体的开发寻求实验物理、热力学和机理基础。这项工作的中心命题，强制执行nontrigonal几何三配位磷配体将产生必要的结构和电子条件，以访问更高的协调磷配体。所追求的具体目标包括以下实验：（1）通过31 P NMR化学位移各向异性分析推断非三角形三配位磷配体配合物的HOMO-LUMO电子结构，（2）开发用于烯烃的催化转化的非旁观者三配位磷配体，所述烯烃涉及正膦和烃基金属膦，和（3）开发非旁观者三配位磷配体配合物作为涉及烷氧基金属膦的醇转化化学的催化剂。这些研究提供了一个详细的，实验量化的影响，非三角形畸变的电子结构在三配位含磷complexes.This奖项反映了NSF的法定使命，并已被认为是值得通过评估使用基金会的智力价值和更广泛的影响审查标准的支持。

With the support of the Chemical Catalysis and the Chemical Structure, Dynamics, and Mechanism B Programs in the Division of Chemistry, Alexander Radosevich of the Department of Chemistry at Massachusetts Institute of Technology is studying the development of new metal-phosphorus complexes as homogeneous catalysts for small molecule conversion chemistry. Catalysis plays a central role in the scalable, economical, and sustainable synthesis of chemicals, including fuels, drugs, and materials. In this project, Dr. Radosevich and his students are creating new metal-based catalysts that bear phosphorus-containing substituents that react in new ways. The specific reactions to be pursued in this research include schemes to convert alkenes and alcohols to value-added products. Graduate and undergraduate researchers working with Dr. Radosevich will receive training in a broad set of spectroscopic, physical, and synthetic chemistry techniques. Achieving these training objectives will contribute to a vital workforce that underpins the economic competitiveness of US-based chemical industries. Dr. Radosevich and his research group participate in a number of outreach efforts advancing the goal of broad participation in science. Dr. Radosevich’s laboratory is also host to visiting international researchers at all levels of experience, contributing to ongoing US leadership in international scientific engagement.Alexander Radosevich and his research team are pursuing the experimental physical, thermodynamic, and mechanistic foundation for the development of new nonspectator ligands based on tricoordinate phosphorus. This work centers on the proposition that enforcing nontrigonal geometries on tricoordinate phosphorus ligands will yield the structural and electronic conditions necessary to access higher-coordinate phosphorus ligands. The specific objectives being pursued comprise experiments that: (1) infer HOMO-LUMO electronic structure of nontrigonal tricoordinate phosphorus ligand complexes through analysis of 31P NMR chemical shift anisotropy, (2) develop nonspectator tricoordinate phosphorus ligands for catalyzed conversions of alkenes involving hydrido- and hydrocarbyl- metallophosphoranes, and (3) develop nonspectator tricoordinate phosphorus ligand complexes as catalysts for alcohol conversion chemistry involving alkoxy metallophosphoranes. These studies are providing a detailed, experimental quantification of the impact of nontrigonal distortion on electronic structure in tricoordinate phosphorus-containing complexes.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.