title: Tandem frustrated Lewis pair/tris(pentafluorophenyl)borane-catalyzed deoxygenative hydrosilylation of carbon dioxide.
abstract: The frustrated Lewis pair system consisting of 2 equiv of 2,2,6,6-tetramethylpiperidine (TMP) and tris(pentafluorophenyl)borane [B(C(6)F(5))(3)] activates carbon dioxide to form a boratocarbamate-TMPH ion pair. In the presence of triethylsilane, this species is converted to a silyl carbamate and the known ion pair [TMPH](+)[HB(C(6)F(5))(3)](-), which recently was shown to react with CO(2) via transfer of the hydride from the hydridoborate to form the formatoborate [TMPH](+)[HC(O)OB(C(6)F(5))(3)](-). In the presence of extra B(C(6)F(5))(3) (0.1-1.0 equiv) and excess triethylsilane, the formatoborate is rapidly hydrosilated to form a formatosilane and regenerate [TMPH](+)[HB(C(6)F(5))(3)](-). The formatosilane in turn is rapidly hydrosilated by the B(C(6)F(5))(3)/Et(3)SiH system to CH(4), with (Et(3)Si)(2)O as the byproduct. At low [Et(3)SiH], intermediate CO(2) reduction products are observed; addition of more CO(2)/Et(3)SiH results in resumed hydrosilylation, indicating that this is a robust, living tandem catalytic system for the deoxygenative reduction of CO(2) to CH(4).
authors.affiliation: Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4.
authors.forename: Andreas
authors.initials: A
authors.lastname: Berkefeld
authors.forename: Warren E
authors.initials: WE
authors.lastname: Piers
authors.forename: Masood
authors.initials: M
authors.lastname: Parvez
mesh_terms: D001880:Boranes / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry; D010880:Piperidines / Q000737:chemistry*; D012821:Silanes / Q000138:chemical synthesis* / Q000737:chemistry; D005466:Fluorocarbons
chemical_list: D001880:Boranes; D002245:Carbon Dioxide; D006845:Hydrocarbons, Fluorinated; D010100:Oxygen; D010880:Piperidines; D012821:Silanes; C528764:2,2,6,6-tetramethyl-1-piperidine; C547049:tris(pentafluorophenyl)borane; D005466:Fluorocarbons