Paramagnetic Ni and Pd complexes have been proposed to play an important role in a number of C-C and C-heteroatom bond formation reactions, as well as a series of oxidative and reductive transformations. In this context, a series of uncommon mononuclear Pd(III) complexes have been synthesized and their oxidative reactivity was investigated. In addition, organometallic Ni(III) complexes relevant to cross-coupling reactions have been isolated and their catalytic reactivity was studied in detail.
Proton-coupled electron transfer (PCET) is a central principle for catalytic hydrogen and CO2 transformations. In this seminar, I will discuss how internal factors of metal–ligand identity, coordination geometry, and spin states interact with external influences such as pKa of proton donors and applied potentials to shape PCET pathways. Our studies with Co complexes show that spin interactions critically govern electron transfer, while investigations of Fe complexes reveal how maintaining the low spin states enables rapid, efficient multi-electron processes.
Abstract. The conversion of inert, energy-poor chemical pollutants into energy-rich chemical fuels represents an attractive solution for the generation of a secure and sustainable energy economy. To date, activation of these substrates is performed industrially via heterogeneous catalysis, often conducted at extreme temperatures and pressures, requiring dedicated facilities. A prominent class of materials invoked in small molecule activation are reducible metal chalcogenides. These materials are composed of metal centers capable of fluctuating between multiple oxidation states.
Abstract: Chemical synthesis driven by electricity offers a scalable, decentralized, and energy-efficient route to furnish value-added products – from fuels to complex molecules. Maximizing reaction efficiency and durability requires immobilized catalytic active sites on electrodes, resulting in dispersed and non-uniform sites. This heterogeneity challenges iterative optimization of reactivity through traditional catalyst modifications, which rely on uniform, singular active sites.
