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.

在该项目中，由化学结构，动力学和机制B计划资助，化学部的b计划，伊利诺伊大学乌尔巴纳 - 尚面aign伊利诺伊大学化学系的Liviu M. Mirica教授旨在发展对磁性性能的电子性质和反应性概况的基本了解。为了实现这一目标，这些研究将利用明智地设计灵活的多层配体的能力，以控制各种氧化态中金属离子的反应性。此外，多种光谱技术和计算研究将应用于这些不常见的顺磁PD系统。他们的努力可能导致从根本上产生新的合成方法，例如，这对于制药行业的过程化学方面具有重要价值。 Professor Liviu M. Mirica will continue to be active in recruiting and training undergradate Students from different backgrounds, either through the St. Elmo Brady Summer Scholars Program and the 3M Summer Scholars Program.In organic 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.这些催化过程中的绝大多数涉及PD（0）和PD（II）氧化物，最近在几种化学转化中调用了PD（IV）氧化物态。相比之下，奇异电子PD（III）和PD（I）氧化物状态的化学尚不清楚。在过去的几年中，Liviu M. Mirica教授的研究小组报告了一系列新型的单核PD（III）和PD（I）复合物的隔离，详细的表征和反应性研究，并由灵活的多耐配体支持。借助了这种不常见的复合物，他们建议详细研究光谱和化学特性，并发现这些奇异电子PD系统的新反应性概况。在该项目中，直接的目标是：（i）对PD（I）复合物进行光谱和机械研究； （iii）探索新的PD（III）/PD（I）介导的化学转化。该奖项反映了NSF的法定任务，并使用基金会的知识分子优点和更广泛的影响评估标准，通过评估诚实地认为支持了支持。

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.