Spectroscopic and Mechanistic Studies of Odd-Electron Palladium Complexes

在这个项目中，由化学部门化学结构、动力学和机制B项目资助，伊利诺伊大学香槟分校化学系的Liviu M. Mirica教授旨在对顺磁性钯（Pd）系统的电子特性和反应性有一个基本的了解。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来控制金属离子在各种氧化状态下的反应性。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教授将继续积极招募和培训来自不同背景的本科生，无论是通过圣埃尔莫·布雷迪暑期学者计划还是3M暑期学者计划。在有机金属催化中，钯配合物作为催化剂在碳-氢官能化、碳-碳和碳杂原子成键反应等广泛的转化中发挥着重要作用。这些催化过程绝大多数涉及Pd(0)和Pd（II）氧化态，最近Pd（IV）氧化态在一些化学转化中被调用。相比之下，奇电子Pd（III）和Pd(I)氧化态的化学性质鲜为人知。在过去的几年中，Liviu M. Mirica教授的研究小组报道了一系列由柔性多齿配体支持的新型单核Pd（III）和Pd(I)配合物的分离、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，以及揭示这些奇电子Pd系统的新反应性。在这个项目中，直接目标是：(i)进行Pd（III）配合物的光谱和机理研究；（ii）进行Pd(I)配合物的光谱和机理研究；（iii）探索新的Pd(iii) /Pd(I)介导的化学转化。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。

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.