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.

在这个由化学部化学合成项目资助的项目中，加州大学圣地亚哥分校的Joshua S. Figueroa教授正在研究配位不饱和过渡金属异氰化物配合物的合成和基本反应性。该项目中将使用的异氰化物分子代表了一类具有显着空间阻碍的分子，因此它们能够有效稳定高度电子和配位不饱和的过渡金属中心。拟议的工作重点是低配位配合物的反应性与异氰化物配体超结构之间的相互作用，以开发过渡金属化学和均相催化中的新反应范式。此外，该项目还非常适合 STEM 教育连续体各个级别的推广和培训。 PI 致力于增加弱势群体 (URP) 参与研究，让年轻学生接触 STEM 领域和职业。 合成工作被纳入 PI 的主要外展工作中，旨在增加合成化学和相关 STEM 领域代表性不足的人员的接触、参与和保留。这些努力包括增加圣地亚哥地区专科转学生对化学研究的参与，以及为以 URP 背景为主的圣地亚哥当地高中学生继续开展化学强化活动。该项目重点关注低配位过渡金属的合成和研究异氰化物配合物，以推进分子设计、小分子活化化学和催化的基本方面。提出了具体的研究，通过合成密切控制过渡金属中心的电子结构环境，以结合和激活极其不反应的小分子底物和难以激活的化学键。提出了一系列合成策略和分子设计原理来实现这些目标。此外，合成工作与先进的光谱、分析、机械和计算技术相结合，以提供对电子结构/反应性相关性的深入了解。