Investigations into the Synthesis and Reactivity of Low-Coordinate Metal Isocyanide Compounds

在化学系化学合成项目的资助下，加州大学圣地亚哥分校的Joshua S. Figueroa教授和他的研究团队通过专注于新型金属化合物的设计、合成和研究，正在开发新的化学转化。人们早就认识到，开发下一代化学工艺的关键是发现具有高反应活性的新化合物。对于工业、农业化学和精细化学的许多重要过程，金属化合物处于生产、选择性和节能化学转化的最前沿。为了保证一个先进的合成化学企业，需要具有新反应活性的金属化合物。该奖项所研究的化合物的一个关键设计特征是用于稳定金属的分子支持基团，也称为配体。这些配体允许精确控制分子几何形状，同时在随后的化学转化中决定选择性。此外，由于存在几个方便的分析标记，这些配体允许容易的产品分析。这项研究强调了氧化亚氮（N2O）的新转化，这是一种强有力的温室气体和环境污染物，但在很大程度上尚未开发用于有机反应。此外，还在研究金属配合物的结构和键合的更基本方面，特别关注金属与碳、氮、氧等元素之间含有多个键的化合物的合成和性质。该奖项的科学工作伴随着向圣地亚哥当地高中学生的推广努力。菲格罗亚教授和他的团队正在让年轻人参与Make &amp； Measure丰富活动。这些努力的目标是鼓励年轻人更多地参与stem相关领域。Figueroa教授正在探索配位和电子不饱和金属异氰化物配合物的合成和反应性。间terphenyl异氰化物配体类被专门用于控制过渡金属中心的分子几何形状和电子结构，以便它们与特定的小分子底物进行选择性反应。此外，分子结构的目标是能够成功地支持晚期过渡金属与碳、氮和氧的多键结合。一个重要的重点放在结合和激活一氧化二氮（N2O）的钴基间三苯异氰化物配合物。一系列独特的钴的n20加合物已经被分离出来，研究的重点是描述这些配合物的反应性，特别注意的是发展到有机底物的温和氧原子转移反应。另一个重点是后期三维过渡金属碳炔配合物的合成和反应性，目标是发展基于合成的转化。合成和实验研究伴随着对圣地亚哥地区高中生的重大推广努力。菲格罗亚教授和他的团队与当地高中合作，让年轻学生参与Make &amp； Measure课外丰富活动。这些活动的重点是让学生接触到先进的过渡金属化学，但他们的总体目标是让年轻人参与到以stem为中心的领域。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 funding from the Chemical Synthesis program of the Division of Chemistry, Professor Joshua S. Figueroa and his research team at the University of California, San Diego are developing new chemical transformations by focusing on the design, synthesis and study of novel metal compounds. It has been long recognized that the key to developing next-generation chemical processes is the discovery of new chemical compounds with high reactivity. For many processes of industrial, agro-chemical and fine-chemical importance, metal compounds lie at the forefront of productive, selective and energy efficient chemical transformations. In order to ensure an advancing synthetic chemistry enterprise, metal compounds capable of new reactivity are required. A key design feature of the compounds under investigation in this award are the molecular supporting groups, also known as ligands, that are used to stabilize the metal. These ligands allow for precise control of molecular geometry, while dictating selectivity in ensuing chemical transformations. In addition, the ligands allow for facile product analysis due to the presence of several convenient analytical markers. This research is emphasizing new transformations of nitrous oxide (N2O), which is a potent greenhouse gas and environmental pollutant, yet is a largely untapped for organic reactions. Also under investigation are more fundamental aspects of structure and bonding in metal complexes, with a specific focus on the synthesis and properties of compounds that contain multiple bonds between metals and elements such as carbon, nitrogen, and oxygen. The scientific work of this award is accompanied by outreach efforts to local San Diego area high school students. Professor Figueroa and his team are engaging young persons in Make & Measure enrichment activities. The goal of these efforts is to stimulate greater participation of young persons in STEM-related fields. Professor Figueroa is exploring the synthesis and reactivity of coordinatively and electronically unsaturated metal isocyanide complexes. The sterically encumbering m-terphenyl isocyanide ligand class is being used specifically to control the molecular geometries and electronic structures of transition metal centers, such that they are primed for selective reactions with specific small molecule substrates. In addition, molecular architectures are being targeted that can successfully support late transition-metal multiple bonding to carbon, nitrogen and oxygen. A significant emphasis is placed on the binding and activation of nitrous oxide (N2O) by cobalt-based m-terphenyl isocyanide complexes. A series of unique N2O-adducts of cobalt have been isolated, and the research is focused on delineating the reactivity available to these complexes, with specific attention being placed on the development of mild oxygen-atom transfer reactions to organic substrates. An additional focus is the synthesis and reactivity of late, 3d transition-metal carbyne complexes, with the goal of developing metathesis-based transformations. The synthetic and experimental research is accompanied by significant outreach efforts to San Diego area high school students. Professor Figueroa and his team have partnered with local high schools to engage young students in Make & Measure extracurricular enrichment activities. These activities focus on exposing students to advanced transition metal chemistry, but their overarching goal is to engage young persons in STEM-centered fields.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.