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.

在这个由化学系化学合成计划资助的项目中，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的合成和基本反应活性。本项目中将使用的异氰化物分子代表了一类具有显著空间阻碍的分子，因此它们在稳定高电子和配位不饱和过渡金属中心方面是有效的。这项工作着眼于低配位络合物的反应性与异氰酸酯配体超结构之间的相互作用，以期在过渡金属化学和均相催化中开发新的反应性范例。此外，该项目也非常适合在STEM教育体系的所有级别开展外展和培训。国际学生协会致力于让代表不足的人(URP)更多地参与研究，使年轻学生接触STEM领域和职业。综合工作被纳入了国际和平协会的主要外联工作，目的是增加在合成化学和相关的STEM领域中任职人数不足的人员的接触、参与和留住。这些努力包括增加圣地亚哥地区大专转学学生对化学研究的参与，并为圣地亚哥当地以URP为主要背景的高中生继续开展化学丰富活动。该项目专注于低配位过渡金属异氰化物的合成和研究，以推进分子设计、小分子活化化学和催化的基础方面。建议进行具体的研究，通过合成来密切控制过渡金属中心的电子结构环境，以结合和激活极不活跃的小分子底物和难以激活的化学键。为了实现这些目标，提出了一系列的合成策略和分子设计原则。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/反应性关联的洞察。