2026 Undergraduate Research Showcase

Formation of Thiolate-Bridged Dinuclear Palladium Complexes and Sulfide-Bridged Trinuclear Palladium Complexes

Document Type

Student Presentation

Presentation Date

4-24-2026

Faculty Sponsor

Dr. Eric Brown

Abstract

The development of efficient hydrogen-based energy systems requires catalysts that can reversibly convert protons and electrons into molecular hydrogen. In nature, this transformation is carried out by hydrogenases, enzymes that employ iron and nickel centers bridged by thiolate ligands. To develop synthetic analogues with greater air stability, we investigated making palladium-centered complexes of the form [(L)2Pd2(μ-SR)2]2+ supported by L = bidentate N-heterocyclic carbene ligand. Our initial efforts with thiolates yielded dimeric butterfly-type structures similar to the geometry of the [FeNi]-hydrogenase, where the R group on the bridging thiolates occupy equatorial positions. To expand this approach, we intended to make complexes of the form [(L)2Pd2(μ-SH)2]2+ by employing hydrosulfide (–SH) ligation in our palladium complexes. Instead of the anticipated dimeric product, we isolated a trinuclear palladium cluster [(L)3Pd3(μ-S)2]2+, confirmed by single-crystal X-ray diffraction. NMR spectroscopy revealed two distinct isomers in solution, with their relative abundance based on solvent polarity and temperature. This work reveals how ligand selectivity directs solution dynamics, while also providing a new framework for constructing palladium complexes that mimic structural features of hydrogenase active sites.

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