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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Precision Selenium Doping Unlocks Palladium Nanocluster for Efficient Chemoselective Hydrogenations.
Xiaojie Hu1, Jiedong Wang1, Tao Liu2,3
1State Key Laboratory of Water Pollution Control and Green Resource Recycling, School of the Environment, Nanjing University, Jiangsu 210023, China.
Journal of the American Chemical Society
|May 15, 2026
Summary
Selenium doping stabilizes palladium nanoclusters for selective hydrogenation of halonitrobenzenes to haloanilines. This method enhances catalyst performance, poison resistance, and reusability in heterogeneous catalysis.
Area of Science:
- Heterogeneous Catalysis
- Nanomaterials Science
- Surface Chemistry
Background:
- Subnanometric metal clusters offer high atom exposure but suffer from strong metal-support interactions, leading to limited selectivity and poor poison resistance.
- Achieving chemoselective transformations with multifunctional substrates remains a challenge in catalysis.
Purpose of the Study:
- To investigate the effect of trace selenium (Se) doping on palladium (Pd) nanocluster electronic states and catalytic performance.
- To enable the chemoselective hydrogenation of halonitrobenzenes to haloanilines using precisely doped Pd nanoclusters.
Main Methods:
- Site-specific doping of trace selenium (Se) onto palladium (Pd) nanoclusters.
- Catalytic testing of Se-doped Pd nanoclusters for halonitrobenzene hydrogenation.
- Mechanistic investigations using spectroscopic and computational methods to correlate electronic state with selectivity.
Main Results:
- Se doping sustained the metallic state (Pd0) of Pd nanoclusters, enhancing selectivity for haloaniline formation (>99%).
- Se-doped Pd catalysts exhibited high turnover frequency (15,593 h-1), excellent poison resistance, and reusability.
- Mechanistic studies revealed Se doping enriches electron density on Pd, improving H2 activation and suppressing hydrodehalogenation.
Conclusions:
- Trace Se doping is a versatile strategy to tune the electronic state of metal nanoclusters and overcome support-induced perturbations.
- This approach provides insights for designing robust and highly selective catalysts for challenging chemical transformations.
