Synthesis and Small-Molecule Reactivity of Unsaturated Metal Isocyanides

不饱和金属异氰化物的合成及小分子反应活性

• 批准号: 1464978
• 负责人: Joshua Figueroa
• 金额: $ 42万
• 依托单位: University of California-San Diego
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-05-01 至 2018-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1464978&HistoricalAwards=false
• 关键词: Synthesis; Small; Molecule; Reactivity; Unsaturated

In this project funded by the Chemical Synthesis program of the Chemistry Division, Professor Joshua S. Figueroa of The University of California, San Diego is studying the synthesis and fundamental reactivity of coordinatively unsaturated transition metal isocyanide complexes. The isocyanide molecules that will be utilized in this project represent a class with significant steric encumbrance, such that they are effective at stabilizing highly electronically and coordinatively unsaturated transition metal centers. The proposed work focuses on the interplay between the reactivity of low-coordinate complexes and isocyanide ligand super-structure for the goal of developing new reactivity paradigms in transition metal chemistry and homogeneous catalysis. In addition, this project is also ideally suited for outreach and training at all levels of the STEM education continuum. The PI is engaged in increasing participation of underrepresented persons (URP) in research to expose young students to STEM fields and careers. The synthetic work is integrated into major outreach efforts of the PI aimed at increasing the exposure, participation and retention of under-represented persons in synthetic chemistry and related STEM fields. These efforts include increasing the participation of junior college transfer students in the San Diego area in chemical research and continued chemistry enrichment activities for local San Diego High School students with predominantly URP backgrounds.This project focuses on the synthesis and study of low-coordinate transition metal isocyanide complexes in order to advance fundamental aspects of molecular design, small-molecule activation chemistry and catalysis. Specific studies are proposed to intimately control the electronic structure environment of transition metal centers, through synthesis, for the binding and activation of exceedingly unreactive small molecule substrates and difficult-to-activate chemical bonds. A complement of synthetic strategies and molecular design principles are proposed to achieve these goals. In addition, the synthetic work is coupled with advanced spectroscopic, analytical, mechanistic and computational techniques to provide insight into electronic-structure/reactivity correlations.

在化学部化学综合计划资助的该项目中，加利福尼亚大学的Joshua S. Figueroa教授正在研究协调不饱和过渡金属异氰化物配合物的综合和基本反应性。该项目中将使用的异氰化物分子代表具有显着空间负担的类别，因此它们有效地稳定高度电子和协调的不饱和过渡金属中心。提出的工作着重于低坐标复合物和异氰化物配体超结构的反应性，目的是在过渡金属化学和均匀催化中开发新的反应性范式。此外，该项目也非常适合在STEM教育连续体的各个级别的外展和培训。 PI致力于增加代表性不足的人（URP）研究，以使年轻学生接触STEM领域和职业。 合成工作融入了PI的主要外展工作，旨在增加代表性不足的人在合成化学和相关茎领域中的暴露，参与和保留。 These efforts include increasing the participation of junior college transfer students in the San Diego area in chemical research and continued chemistry enrichment activities for local San Diego High School students with predominantly URP backgrounds.This project focuses on the synthesis and study of low-coordinate transition metal isocyanide complexes in order to advance fundamental aspects of molecular design, small-molecule activation chemistry and catalysis.提出了特定的研究，以通过合成，直接控制过渡金属中心的电子结构环境，以结合和激活极具反应性的小分子底物和难以激活的化学键。提出了综合策略和分子设计原则的补充，以实现这些目标。此外，合成工作还与高级光谱，分析，机械和计算技术相结合，以洞悉电子结构/反应性相关性。