biostudies-literature00470Anderson AEEngineering and Physical Sciences Research Council154-163https://www.ebi.ac.uk/biostudies/studies/S-EPMC6566290biostudies-literatureUnknown148(1)<h4>Abstract</h4>The versatility of MOFs as highly porous Lewis acidic supports for precious metal nanoparticles has been exploited for one-pot tandem reductive amination catalysis. MIL-101(Cr) loaded with Pd nanoparticles ca. 3 nm in size at 0.2-1 wt% has been used to catalyse the reaction of 4'-fluoroacetophenone with benzylamine under 10 bar of H₂ to give the secondary amine, 4'-fluoro-α-methyl-<i>N</i>-phenylmethylbenzenemethanamine. For the highest Pd loading, major hydrogenolysis of the secondary amine occurs in a second tandem reaction, but by changing the ratio of Pd to Lewis acidic Cr³⁺ active sites it is possible to tune the catalytic selectivity to the desired 2° amine product. An empirical kinetic analysis was performed to demonstrate this active site complementarity.<h4>Graphical abstract</h4>Catalysis lettersTuning Pd-nanoparticle@MIL-101(Cr) Catalysts for Tandem Reductive Amination.PMC6566290EP/L505079/11398548Anderson AEWright PABaddeley CJ47falseTuning Pd-nanoparticle@MIL-101(Cr) Catalysts for Tandem Reductive Amination.<h4>Abstract</h4>The versatility of MOFs as highly porous Lewis acidic supports for precious metal nanoparticles has been exploited for one-pot tandem reductive amination catalysis. MIL-101(Cr) loaded with Pd nanoparticles ca. 3 nm in size at 0.2-1 wt% has been used to catalyse the reaction of 4'-fluoroacetophenone with benzylamine under 10 bar of H₂ to give the secondary amine, 4'-fluoro-α-methyl-<i>N</i>-phenylmethylbenzenemethanamine. For the highest Pd loading, major hydrogenolysis of the secondary amine occurs in a second tandem reaction, but by changing the ratio of Pd to Lewis acidic Cr³⁺ active sites it is possible to tune the catalytic selectivity to the desired 2° amine product. An empirical kinetic analysis was performed to demonstrate this active site complementarity.<h4>Graphical abstract</h4>2018-01-01T00:00:00Z20182024-11-20T06:46:31.379Z2019-07-24T07:17:39ZS-EPMC65662903125828610.1007/s10562-017-2208-0