Spectroscopic and Mechanistic Studies of Odd-Electron Palladium Complexes

奇电子钯配合物的光谱和机理研究

• 批准号: 2102544
• 负责人: Liviu Mirica
• 金额: $ 48.2万
• 依托单位: University of Illinois at Urbana-Champaign
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-07-01 至 2024-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102544&HistoricalAwards=false
• 关键词: Spectroscopic; Mechanistic; Studies; Odd; Electron

In this project, funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Professor Liviu M. Mirica of the Department of Chemistry at the University of Illinois at Urbana-Champaign aims to develop a fundamental understanding of the electronic properties and reactivity profiles of paramagnetic palladium(Pd)systems. Toward this goal, these studies will take advantage of the ability to judiciously design flexible multidentate ligands that control the reactivity of metal ions in various oxidation states. In addition, a wide range of spectroscopic techniques and computational studies will be applied to studying in detail these uncommon paramagnetic Pd systems. Their efforts could lead to fundamentally new synthetic methods, which are of great value for the process chemistry side of the pharmaceutical industry, for example. Professor Liviu M. Mirica will continue to be active in recruiting and training undergraduate students from different backgrounds, either through the St. Elmo Brady Summer Scholars Program and the 3M Summer Scholars Program.In organometallic catalysis, palladium complexes play an important role as catalysts for a wide range of transformations such as carbon-hydrogen functionalization as well as carbon-carbon and carbon-heteroatom bond forming reactions. The vast majority of these catalytic processes involve Pd(0) and Pd(II) oxidation states, and more recently the Pd(IV) oxidation state has been invoked in several chemical transformations. By contrast, the chemistry of the odd-electron Pd(III) and Pd(I) oxidation states is much less known. During the past several years, Professor Liviu M. Mirica’s research group has reported the isolation, detailed characterization, and reactivity studies of a series of novel mononuclear Pd(III) and Pd(I) complexes supported by flexible multidentate ligands. With such uncommon complexes in hand, they propose to investigate in detail the spectroscopic and chemical properties, as well as uncover new reactivity profiles for these odd-electron Pd systems. In this project, the immediate objectives are to: (i) perform spectroscopic and mechanistic studies of Pd(III) complexes; (ii) perform spectroscopic and mechanistic studies of Pd(I) complexes; and (iii) explore new Pd(III)/Pd(I)–mediated chemical transformations.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.

本课题由化学系化学结构、动力学机制B项目资助，由Liviu M.伊利诺伊大学厄巴纳-香槟分校化学系的Mirica旨在对顺磁钯（Pd）系统的电子性质和反应性特征进行基本了解。为了实现这一目标，这些研究将利用明智地设计灵活的多齿配体的能力，控制各种氧化态的金属离子的反应性。此外，广泛的光谱技术和计算研究将被应用于详细研究这些不常见的顺磁Pd系统。 他们的努力可能会带来全新的合成方法，例如，这对制药工业的过程化学方面具有重要价值。Liviu M. Mirica将继续通过圣埃尔莫布雷迪暑期奖学金项目和3 M暑期奖学金项目，积极招收和培训来自不同背景的本科生。在有机金属催化领域，钯配合物作为催化剂在碳氢官能化、碳碳键和碳杂原子键形成反应等广泛的转化中发挥着重要作用。这些催化过程中的绝大多数涉及Pd（0）和Pd（II）氧化态，并且最近在几种化学转化中已经调用了Pd（IV）氧化态。相比之下，奇电子Pd（III）和Pd（I）氧化态的化学性质知之甚少。在过去的几年里，Liviu M. Mirica的研究小组报告了一系列由柔性多齿配体支持的新型单核Pd（III）和Pd（I）络合物的分离、详细表征和反应性研究。有了这些不常见的配合物，他们建议详细研究光谱和化学性质，并发现这些奇电子Pd系统的新反应性特征。该项目的近期目标是：（一）对钯（三）络合物进行光谱和机理研究;（二）对钯（一）络合物进行光谱和机理研究;和（iii）探索新的Pd（III）/Pd（I）-该奖项反映了NSF的法定使命，并被认为是值得通过使用基金会的知识价值和更广泛的影响审查评估的支持的搜索.

项目成果

Isolation and Characterization of Heteroleptic Mononuclear Palladium(I) Complexes

• DOI: 10.1021/jacs.2c08765
• 发表时间: 2022-10-18
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Tran, Giang N.;Bouley, Bailey S.;Mirica, Liviu M.
• 通讯作者: Mirica, Liviu M.

Allylic Amination of Pd(II)-Allyl Complexes via High-Valent Pd Intermediates

• DOI: 10.1021/acs.organomet.2c00215
• 发表时间: 2022-07-12
• 期刊: ORGANOMETALLICS
• 影响因子: 2.8
• 作者: Wang，Yung-Ching;Rath，Nigam P.;Mirica，Liviu M.
• 通讯作者: Mirica，Liviu M.