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Synthesis, Reactivity, and Photochemistry of Late Transition Metal Complexes Featuring Carbenium-based Ambiphilic Ligands

以碳基两亲配体为特征的后过渡金属配合物的合成、反应性和光化学

基本信息

批准号：
2154972
负责人：
Francois Gabbai
金额：
$ 55万
依托单位：
Texas A&M University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2022
资助国家：
美国
起止时间：
2022-08-01 至 2025-07-31
项目状态：
未结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154972&HistoricalAwards=false
关键词：
Synthesis Reactivity Photochemistry Late Transition

项目摘要

With the support of the Chemical Synthesis program of the Division of Chemistry, Professor François Gabbaï of the Department of Chemistry at Texas A&M University will investigate a new family of ligands containing a positively charged carbon unit positioned next to a metal-binding site. Ligands are molecular compounds designed to hold metal atoms and influence their ability to carry out and accelerate chemical reactions. These are essential to a broad range of chemical industries. Designing new ligands that can purposefully ameliorate the reactivity of metals is thus an important line of inquiry. The new ligands prepared in this research are designed to allow for a positively charged carbon unit to approach or combine with a metal atom, enhancing its reactivity. Next, the ligand-metal complexes are to be developed into platforms for the generation of solar fuels, thus impacting research on new energy storage strategies. In addition, the project will provide mentorship to diverse high school students and and present chemical knowledge to K-6 grade students in two-way dual language programs integrating native English and native Spanish.This project from the Gabbaï team at Texas A & M will investigate the synthesis and coordination chemistry of ambiphilic ligands featuring a carbenium ion positioned next to a phosphine- or carbene-based metal-binding site. Coordination of these ligands to late transition metals such as nickel, palladium, platinum, and gold affords a family of complexes in which the late transition metal is electronically impoverished via the formation of a charge transfer or electrostatic interaction between the metal and the carbenium unit. These atypical interactions will be characterized using structural, spectroscopic, and computational tools. The knowledge derived from these investigations is expected to provide a framework for the fine-tuning of metal-ligand interactions and provide organometallic chemists with new ways to influence the reactivity of late transition metal centers. If successful, these studies will lead to new opportunities in halogen photoreductive elimination chemistry and in carbophilic catalysis.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支持下，德克萨斯农工大学化学系的franois教授Gabbaï将研究一个新的配体家族，该配体包含一个位于金属结合位点旁边的带正电的碳单元。配体是一种分子化合物，用来容纳金属原子，并影响它们进行和加速化学反应的能力。这些对广泛的化学工业都是必不可少的。因此，设计能够有目的地改善金属反应性的新配体是一条重要的研究路线。本研究中制备的新配体旨在允许带正电的碳单元接近或与金属原子结合，增强其反应性。接下来，这些配金属配合物将被开发成太阳能燃料的生产平台，从而影响新的储能策略的研究。此外，该项目将为不同的高中学生提供指导，并通过英语和西班牙语的双向双语课程向K-6年级的学生传授化学知识。这个项目来自德克萨斯州a&m的Gabbaï团队，将研究两亲性配体的合成和配位化学，其特征是位于磷化氢或碳基金属结合位点旁边的碳离子。这些配体与晚期过渡金属如镍、钯、铂和金的配位提供了一系列配合物，其中晚期过渡金属通过金属与碳单元之间电荷转移或静电相互作用的形成而在电子上被剥夺。这些非典型相互作用将使用结构、光谱和计算工具进行表征。从这些研究中获得的知识有望为金属-配体相互作用的微调提供一个框架，并为有机金属化学家提供影响晚期过渡金属中心反应性的新方法。如果成功，这些研究将为卤素光还原消除化学和亲碳催化带来新的机遇。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。