Influence of the Base on Pd@MIL-101-NH2(Cr) as Catalyst for the Suzuki–Miyaura Cross-Coupling Reaction

DOI: 10.1002/chem.201500843

Authors: Fabian Carson (Stockholm University) , Vlad Pascanu (Stockholm University) , Antonio Bermejo Gómez  (Stockholm University) , Yi Zhang  (Stockholm University) , Ana Platero-prats (Stockholm University) , Xiaodong Zou (Stockholm University) , Belén Martín-matute  (Stockholm University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry - A European Journal , VOL 21 (30) , PAGES 10896 - 10902

State: Published (Approved)
Published: July 2015
Diamond Proposal Number(s): 12120

Abstract: The chemical stability of metal–organic frameworks (MOFs) is a major factor preventing their use in industrial processes. Herein, it is shown that judicious choice of the base for the Suzuki–Miyaura cross-coupling reaction can avoid decomposition of the MOF catalyst Pd@MIL-101-NH2 (Cr). Four bases were compared for the reaction: K2CO3, KF, Cs2CO3 and CsF. The carbonates were the most active and achieved excellent yields in shorter reaction times than the fluorides. However, powder XRD and N2 sorption measurements showed that the MOF catalyst was degraded when carbonates were used but remained crystalline and porous with the fluorides. XANES measurements revealed that the trimeric chromium cluster of Pd@MIL-101-NH2 (Cr) is still present in the degraded MOF. In addition, the different countercations of the base significantly affected the catalytic activity of the material. TEM revealed that after several catalytic runs many of the Pd nanoparticles (NPs) had migrated to the external surface of the MOF particles and formed larger aggregates. The Pd NPs were larger after catalysis with caesium bases compared to potassium bases.

Journal Keywords: cross-coupling ; heterogeneous catalysis; metal– organic frameworks; nanoparticles; palladium

Subject Areas: Chemistry


Instruments: B18-Core EXAFS