Synthesis and Small-Molecule Reactivity of Unsaturated Metal Isocyanides

加州大学圣地亚哥分校的Joshua S. Figueroa教授在化学部化学合成项目资助下，研究了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。在这个项目中使用的异氰化物分子代表了一类具有显著空间负担的分子，因此它们在稳定高度电子和配位不饱和过渡金属中心方面是有效的。本文的工作重点是研究低配位配合物的反应活性与异氰化物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发展新的反应活性范式。此外，该项目也非常适合STEM教育连续体的各级外展和培训。PI致力于增加代表性不足的人（URP）参与研究，使年轻学生接触STEM领域和职业。合成工作被纳入PI的主要外展工作，旨在增加合成化学和相关STEM领域中代表性不足的人员的曝光、参与和保留。这些努力包括增加圣地亚哥地区大专转校生对化学研究的参与，并继续为圣地亚哥当地高中学生提供化学丰富活动，主要是URP背景。本项目致力于低配位过渡金属异氰化物配合物的合成和研究，以推进分子设计、小分子活化化学和催化的基础研究。提出了具体的研究，以密切控制过渡金属中心的电子结构环境，通过合成，结合和激活极不活泼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，提供了对电子结构/反应性相关性的洞察。

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.