title: Selective catalytic behavior of a phosphine-tagged metal-organic framework organocatalyst.
abstract: Steric hindrance by a metal-organic framework (MOF) is shown to influence the outcome of a catalytic reaction by controlling the orientation of its intermediates. This is demonstrated using an organocatalyst, phosphine MOF LSK-3, which is evaluated with the aid of molecular modeling and NMR spectroscopy techniques. This report is the first application of phosphine MOFs in organocatalysis and explores the potential of a framework steric hindrance to impose selectivity on a catalytic reaction. These findings expand the opportunities for control and design of the active site in the pocket of heterogeneous catalysts.
authors.affiliation: Department of Chemistry and Applied Biosciences, Laboratory of Chemical and Bioengineering, ETH Zurich, 8093 Zürich (Switzerland); Department of Synchrothron Radiation, Laboratory for Catalysis and Sustainable Chemistry, Paul Scherrer Institute, 5232 Villigen PSI (Switzerland).
authors.forename: Xiaoying
authors.initials: X
authors.lastname: Xu
authors.forename: Stephan M
authors.initials: SM
authors.lastname: Rummelt
authors.forename: Flavien L
authors.initials: FL
authors.lastname: Morel
authors.forename: Marco
authors.initials: M
authors.lastname: Ranocchiari
authors.forename: Jeroen A
authors.initials: JA
authors.lastname: van Bokhoven
mesh_terms: D002384:Catalysis; D003374:Coumarins / Q000138:chemical synthesis / Q000737:chemistry; D061565:Cycloaddition Reaction; D009682:Magnetic Resonance Spectroscopy; D009942:Organometallic Compounds / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D003374:Coumarins; D009942:Organometallic Compounds; D010720:Phosphines; C030123:coumarin; C044646:phosphine
keywords: heterogeneous catalysis; metal-organic frameworks; organocatalysis; phosphines; selectivity