title: Ambiphilic Frustrated Lewis Pair Exhibiting High Robustness and Reversible Water Activation: Towards the Metal-Free Hydrogenation of Carbon Dioxide.
abstract: The synthesis and structural characterization of a phenylene-bridged Frustrated Lewis Pair (FLP) having a 2,2,6,6‑tetramethylpiperidine (TMP) as the Lewis base and a 9-borabicyclo[3.3.1]nonane (BBN) as the Lewis acid is reported. This FLP exhibits unique robustness towards the products of carbon dioxide hydrogenation. The compound shows reversible splitting of water, formic acid and methanol while no reaction is observed in the presence of excess formaldehyde. The molecule is incredibly robust, showing little sign of degradation after heating at 80 °C in benzene with 10 equiv. of formic acid for 24 h. The robustness of the system could be exploited in the design of metal-free catalysts for the hydrogenation of carbon dioxide.
authors.affiliation: Department of Chemistry, Centre de Catalyse et Chimie Verte (C3V), Université Laval, 1045 Avenue de la Médecine, Québec, QC G1V 0A6, Canada. etienne.rochette.2@ulaval.ca.
authors.forename: Étienne
authors.initials: É
authors.lastname: Rochette
authors.affiliation: Department of Chemistry, Centre de Catalyse et Chimie Verte (C3V), Université Laval, 1045 Avenue de la Médecine, Québec, QC G1V 0A6, Canada. marc-andre.courtemanche.1@ulaval.ca.
authors.forename: Marc-André
authors.initials: MA
authors.lastname: Courtemanche
authors.affiliation: Department of Chemistry, University of Toronto, 80 George Street, Toronto, ON M5S 3H6, Canada. alex.pulis@utoronto.ca.
authors.forename: Alexander P
authors.initials: AP
authors.lastname: Pulis
authors.affiliation: Department of Chemistry, Centre de Catalyse et Chimie Verte (C3V), Université Laval, 1045 Avenue de la Médecine, Québec, QC G1V 0A6, Canada. bi.wenhua.1@ulaval.ca.
authors.forename: Wenhua
authors.initials: W
authors.lastname: Bi
authors.affiliation: Department of Chemistry, Centre de Catalyse et Chimie Verte (C3V), Université Laval, 1045 Avenue de la Médecine, Québec, QC G1V 0A6, Canada. frederic.fontaine@chm.ulaval.ca.
authors.forename: Frédéric-Georges
authors.initials: FG
authors.lastname: Fontaine
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006859:Hydrogen / Q000737:chemistry*; D008958:Models, Molecular; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water; D002245:Carbon Dioxide; D006859:Hydrogen
keywords: Frustrated Lewis Pairs; Lewis acid; ambiphilic molecules; carbon dioxide; catalysis; hydrogenation