Spectroscopic and Mechanistic Studies of Odd-Electron Palladium Complexes

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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.