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

低配位金属异氰化物的合成及反应活性研究

基本信息

批准号：
1802646
负责人：
Joshua Figueroa
金额：
$ 45万
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：
2018
资助国家：
美国
起止时间：
2018-08-01 至 2023-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1802646&HistoricalAwards=false
关键词：
Investigations into Synthesis Reactivity Low

项目摘要

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.

在化学系化学合成项目的资助下，约书亚S.菲格罗亚和他在加州大学圣地亚哥分校的研究团队正在通过专注于新型金属化合物的设计、合成和研究来开发新的化学转化。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性的新化合物。对于工业、农业化学和精细化学品的许多重要过程，金属化合物处于生产性、选择性和节能化学转化的最前沿。为了确保合成化学事业的发展，需要具有新反应性的金属化合物。该奖项所研究的化合物的一个关键设计特征是分子支撑基团，也称为配体，用于稳定金属。这些配体允许精确控制分子几何形状，同时决定随后的化学转化的选择性。此外，由于存在几种方便的分析标记物，配体允许容易的产物分析。这项研究强调了一氧化二氮（N2 O）的新转化，这是一种潜在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。金属络合物的结构和键合的更基本方面也在研究中，特别关注含有金属和元素（如碳，氮和氧）之间多重键的化合物的合成和性质。该奖项的科学工作是伴随着推广工作，以当地圣地亚哥地区的高中学生。Figueroa教授和他的团队正在让年轻人参与Make Measure丰富活动。这些努力的目标是鼓励年轻人更多地参与科学、技术、工程和数学相关领域。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。空间位阻的间三联苯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，使得它们被引导用于与特定小分子底物的选择性反应。此外，分子结构正在成为目标，可以成功地支持后过渡金属与碳，氮和氧的多重键合。一个显着的重点放在一氧化二氮（N2 O）的钴基间三联苯异腈配合物的结合和激活。一系列独特的N2 O-加合物的钴已被隔离，研究的重点是描绘这些配合物的反应性，特别注意被放置在温和的氧原子转移反应的有机基板的发展。另一个重点是后期3d过渡金属碳炔配合物的合成和反应性，目标是开发基于易位的转化。合成和实验研究是伴随着重大的推广工作，以圣地亚哥地区的高中学生。菲格罗亚教授和他的团队与当地高中合作，让年轻学生参与课外活动。这些活动的重点是让学生接触先进的过渡金属化学，但其总体目标是让年轻人参与以STEM为中心的领域。该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

期刊论文数量（17）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Side-On Coordination of Nitrous Oxide to a Mononuclear Cobalt Center

DOI：
10.1021/jacs.9b08241
发表时间：
2019-09-25
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
影响因子：
15
作者：
Mokhtarzadeh, Charles C.;Chan, Chinglin;Figueroa, Joshua S.
通讯作者：
Figueroa, Joshua S.

Three-coordinate monoanions of rhodium(1–) and iridium(1–): Isolable examples of coordinatively-unsaturated metalate anions

铑(1-) 和铱(1-) 的三配位单阴离子：配位不饱和金属阴离子的可分离实例

DOI：
10.1016/j.poly.2023.116565
发表时间：
2023
期刊：
Polyhedron
影响因子：
2.6
作者：
Neville, Michael L.;Chan, Chinglin;Barnett, Brandon R.;Hernandez, Ritchie E.;Moore, Curtis E.;Figueroa, Joshua S.
通讯作者：
Figueroa, Joshua S.

Rhenium Complexes with p‐Fluorophenylisocyanide

铼与对氟苯基异氰化物的配合物

DOI：
10.1002/zaac.202200320
发表时间：
2022
期刊：
Zeitschrift für anorganische und allgemeine Chemie
影响因子：
0
作者：
Claude, Guilhem;Weh, Dominik;Hagenbach, Adelheid;Figueroa, Joshua S.;Abram, Ulrich
通讯作者：
Abram, Ulrich

A Complete Triad of Zero‐Valent 17‐Electron Monoradicals of Group 7 Elements Stabilized by m ‐Terphenyl Isocyanides

间·三联苯异氰化物稳定的第 7 族元素的完整零价 17 价电子单价基团

DOI：
10.1002/anie.202300254
发表时间：
2023
期刊：
Angewandte Chemie International Edition
影响因子：
0
作者：
Salsi, Federico;Wang, Shuai;Teutloff, Christian;Busse, Marvin;Neville, Michael L.;Hagenbach, Adelheid;Bittl, Robert;Figueroa, Joshua S.;Abram, Ulrich
通讯作者：
Abram, Ulrich

Terminal coordination of diatomic boron monofluoride to iron