Tuning Pd-nanoparticle@MIL-101(Cr) catalysts for tandem reductive amination

Amanda E. Anderson; Christopher J. Baddeley; Paul A. Wright

doi:10.1007/s10562-017-2208-0

Tuning Pd-nanoparticle@MIL-101(Cr) catalysts for tandem reductive amination

Amanda E. Anderson, Christopher J. Baddeley, Paul A. Wright

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Abstract

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-N-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.

Original language	English
Journal	Catalysis Letters
Volume	In press
DOIs	https://doi.org/10.1007/s10562-017-2208-0
Publication status	Published - 27 Nov 2017

Keywords

Pd@MIL-101
Tandem reductive amination
Kinetic modelling

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Cite this

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title = "Tuning Pd-nanoparticle@MIL-101(Cr) catalysts for tandem reductive amination",

abstract = "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-N-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.",

keywords = "Pd@MIL-101, Tandem reductive amination, Kinetic modelling",

author = "Anderson, {Amanda E.} and Baddeley, {Christopher J.} and Wright, {Paul A.}",

note = "The authors thank the EPSRC (EP/L505079/1), SASOL Technology UK and the University of St Andrews for funding.",

year = "2017",

month = nov,

day = "27",

doi = "10.1007/s10562-017-2208-0",

language = "English",

volume = "In press",

journal = "Catalysis Letters",

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TY - JOUR

T1 - Tuning Pd-nanoparticle@MIL-101(Cr) catalysts for tandem reductive amination

AU - Anderson, Amanda E.

AU - Baddeley, Christopher J.

AU - Wright, Paul A.

N1 - The authors thank the EPSRC (EP/L505079/1), SASOL Technology UK and the University of St Andrews for funding.

PY - 2017/11/27

Y1 - 2017/11/27

N2 - 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-N-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.

AB - 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-N-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.

KW - Pd@MIL-101

KW - Tandem reductive amination

KW - Kinetic modelling

UR - https://link.springer.com/article/10.1007%2Fs10562-017-2208-0#SupplementaryMaterial

U2 - 10.1007/s10562-017-2208-0

DO - 10.1007/s10562-017-2208-0

M3 - Article

SN - 1011-372X

VL - In press

JO - Catalysis Letters

JF - Catalysis Letters

ER -

Tuning Pd-nanoparticle@MIL-101(Cr) catalysts for tandem reductive amination

Abstract

Keywords

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