Metal-Organic Framework Surface Functionalization Enhancing the Activity and Stability of Palladium Nanoparticles for Carbon-Halogen Bond Activation

Yida Wu; Xiao Feng; Qixiang Zhai; Haosen Wang; Huanfeng Jiang; Yanwei Ren

doi:10.1021/acs.inorgchem.2c00379

Metal-Organic Framework Surface Functionalization Enhancing the Activity and Stability of Palladium Nanoparticles for Carbon-Halogen Bond Activation

Inorg Chem. 2022 May 9;61(18):6995-7004. doi: 10.1021/acs.inorgchem.2c00379. Epub 2022 Apr 28.

Authors

Yida Wu¹, Xiao Feng¹, Qixiang Zhai¹, Haosen Wang¹, Huanfeng Jiang¹, Yanwei Ren¹

Affiliation

¹ Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510641 Guangdong, P. R. China.

PMID: 35482971
DOI: 10.1021/acs.inorgchem.2c00379

Abstract

Supported metal nanocatalyst is one of the efficient tools for organic transformations. However, catalyst deactivation caused by the migration, aggregation, and leaching of active metal species in the reaction process remains challenging. Herein, a metal-organic framework (MOF), MIL-101, was employed to covalently graft the PPh₃ ligand on its surface and then supported palladium nanoparticles (Pd NPs), affording Pd/MIL-101-PPh₃. A variety of spectral characterizations and DFT calculation reveal that there is an electron-donating effect of the MOF surface PPh₃ toward Pd NPs, which markedly boosts the activation of the carbon-halogen bond in aryl halides. Consequently, Pd/MIL-101-PPh₃ exhibits excellent activity for the three-component reaction of 2-iodoaniline, CO₂, and isocyanide, as well as Suzuki-Miyaura and Heck coupling reactions, far exceeding amino-functionalized Pd/MIL-101-NH₂, naked Pd/MIL-101, and other commercial-supported Pd catalysts. Furthermore, Pd/MIL-101-PPh₃ can also frustrate the migration, aggregation, and leaching of reactive Pd species in the reaction process due to the molecular fence effect generated by MOF surface functionalization.