Two-Electron Photoreduction of Pd(II) Oxalates: In Crystallo Synthesis and Catalysis
6 affiliations
- 1Department of Chemistry
- 2Texas A&M University
- 3University of Pennsylvania
- 4Argonne National Laboratory
- 5University of Chicago
- 6Center for Nanoscale Materials
Abstract
Discovery and optimization of cross-coupling catalysts require catalyst activation strategies that balance the operational simplicity of air-stable precatalysts with the need for air-sensitive, lowcoordinate and -valent intermediates for substrate activation and turnover. Here we introduce a general approach for on-demand catalyst activation via two-electron photoreduction of air-stable phosphine-ligated palladium(II) oxalates. The platform exploits rapid ligand exchange at (MeCN)2Pd(ox) to enable modular assembly of catalyst photoprecursors from a single precursor. In crystallo photochemistry and single-crystal Raman spectroscopy of phosphine-supported Pd oxalates establish that photoactivation proceeds via the extrusion of two molecules of CO2 and provide the Uirst crystallographic characterization of a Pd–CO2 adduct. Two-electron photoactivation translates to the solution phase to provide a platform to access Pd oxidative addition complexes (OACs) and to generate poison-free, on-cycle catalyst intermediates. The combination of rapid and quantitative ligand exchange coupled with facile two-electron photoreduction enables application in highthroughput experimentation (HTE) workUlows and on-plate ligand screening. Photogenerated catalysts are competitive with state-of-the-art precatalysts in both C–N cross-coupling and a newly developed base-free Suzuki reaction. These results establish Pd oxalates as general, photoactivated precursors to unsaturated catalyst intermediates that unlock streamlined, combinatorial workUlows for catalyst discovery and data-driven optimization.
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BibTeX
@misc{sur2026twoelectron,
title = {{Two-Electron Photoreduction of Pd(II) Oxalates: In Crystallo Synthesis and Catalysis}},
author = {Aishanee Sur and Pritam Roychowdhury and Subham Sarkar and Matthew T. Figgins and Saim Waheed and Yu-Sheng Chen and David J. Gosztola and Nattamai Bhuvanesh and Andrew F. Zahrt and David C. Powers},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010046/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010046/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Two-Electron Photoreduction of Pd(II) Oxalates: In Crystallo Synthesis and Catalysis
AU - Aishanee Sur
AU - Pritam Roychowdhury
AU - Subham Sarkar
AU - Matthew T. Figgins
AU - Saim Waheed
AU - Yu-Sheng Chen
AU - David J. Gosztola
AU - Nattamai Bhuvanesh
AU - Andrew F. Zahrt
AU - David C. Powers
PY - 2026
DA - 2026/10/07
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010046/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010046/v1
AB - Discovery and optimization of cross-coupling catalysts require catalyst activation strategies that balance the operational simplicity of air-stable precatalysts with the need for air-sensitive, lowcoordinate and -valent intermediates for substrate activation and turnover. Here we introduce a general approach for on-demand catalyst activation via two-electron photoreduction of air-stable phosphine-ligated palladium(II) oxalates. The platform exploits rapid ligand exchange at (MeCN)2Pd(ox) to enable modular assembly of catalyst photoprecursors from a single precursor. In crystallo photochemistry and single-crystal Raman spectroscopy of phosphine-supported Pd oxalates establish that photoactivation proceeds via the extrusion of two molecules of CO2 and provide the Uirst crystallographic characterization of a Pd–CO2 adduct. Two-electron photoactivation translates to the solution phase to provide a platform to access Pd oxidative addition complexes (OACs) and to generate poison-free, on-cycle catalyst intermediates. The combination of rapid and quantitative ligand exchange coupled with facile two-electron photoreduction enables application in highthroughput experimentation (HTE) workUlows and on-plate ligand screening. Photogenerated catalysts are competitive with state-of-the-art precatalysts in both C–N cross-coupling and a newly developed base-free Suzuki reaction. These results establish Pd oxalates as general, photoactivated precursors to unsaturated catalyst intermediates that unlock streamlined, combinatorial workUlows for catalyst discovery and data-driven optimization.
ER -