Nonspectator Phosphorus Ligands for Catalysis

在化学催化和化学结构、动力学和机理B项目的支持下，麻省理工学院化学系的Alexander Radosevich正在研究开发新型金属-磷配合物作为小分子转化化学的均相催化剂。催化在大规模、经济和可持续的化学合成中起着核心作用，包括燃料、药物和材料。在这个项目中，Radosevich博士和他的学生们正在创造新的金属基催化剂，这种催化剂含有含磷取代基，可以以新的方式反应。本研究中要进行的具体反应包括将烯烃和醇转化为增值产品的方案。与Radosevich博士一起工作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方面的培训。实现这些培训目标将有助于培养一支至关重要的劳动力队伍，从而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许多推广工作，以推进广泛参与科学的目标。Radosevich博士的实验室还接待了各种经验水平的国际访问研究人员，为美国在国际科学参与中的持续领导地位做出了贡献。Alexander Radosevich和他的研究团队正在为开发基于三坐标磷的新型非旁观者配体寻找实验物理、热力学和机械基础。这项工作的中心命题是，在三坐标磷配体上强制非三角几何将产生获得高坐标磷配体所需的结构和电子条件。所追求的具体目标包括以下实验：(1)通过分析31P核磁共振化学位移各向异性，推断出非三角三配位磷配合物的HOMO-LUMO电子结构；(2)开发出非旁观者三配位磷配合物，用于催化烃基和烃基金属磷烷的烯烃转化；(3)开发出非旁观者三配位磷配合物，用于催化烷氧基金属磷烷的醇转化化学。这些研究提供了详细的、实验量化的非三角畸变对三坐标含磷配合物电子结构的影响。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。

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.