title: The Chemistry of a Non-Interacting Vicinal Frustrated Phosphane/Borane Lewis Pair.
abstract: The dimesitylphosphinocyclopentene/HB(C6F5)2-derived vicinal trans-1,2-P/B frustrated Lewis pair (FLP) 4 shows no direct phosphane-borane interaction. Toward some reagents it behaves similar to an intermolecular FLP; it cleaves dihydrogen, deprotonates terminal alkynes, and adds to organic carbonyl compounds including CO2. It shows typical intramolecular FLP reaction modes (cooperative 1,1-additions) to mesityl azide, to carbon monoxide, and to NO. The latter reaction yields a persistent P/B FLPNO nitroxide radical, which undergoes H-atom abstraction reactions. The FLP 4 serves as a template for the CO reduction by [HB(C6F5)2] to generate a FLP-η2-formylborane. The formylborane moiety is removed from the FLP template by reaction with pyridine to yield a genuine pyridine stabilized formylborane that undergoes characteristic borane carbaldehyde reactions (Wittig olefination, imine formation). Most new products were characterized by X-ray diffraction.
authors.affiliation: Organisch-Chemisches Institut, Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Lisa-Maria
authors.initials: LM
authors.lastname: Elmer
authors.affiliation: Organisch-Chemisches Institut, Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Gerald
authors.initials: G
authors.lastname: Kehr
authors.affiliation: Organisch-Chemisches Institut, Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Constantin G
authors.initials: CG
authors.lastname: Daniliuc
authors.affiliation: Institut für Physikalische Chemie, Universutät Münster, Corrensstraße 28/30, 48149, Münster, Germany.
authors.forename: Melanie
authors.initials: M
authors.lastname: Siedow
authors.affiliation: Institut für Physikalische Chemie, Universutät Münster, Corrensstraße 28/30, 48149, Münster, Germany.|Instituto de Física Sao Carlos, Universidade de Sao Paulo, CP 369, 13560-970, Sao Carlos, SP, Brasil.
authors.forename: Hellmut
authors.initials: H
authors.lastname: Eckert
authors.affiliation: Organisch-Chemisches Institut, Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Matthias
authors.initials: M
authors.lastname: Tesch
authors.affiliation: Organisch-Chemisches Institut, Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Armido
authors.initials: A
authors.lastname: Studer
authors.affiliation: Georgetown University, Department of Chemistry, Box 571227, Washington DC, 20057-1227, USA.
authors.forename: Kamille
authors.initials: K
authors.lastname: Williams
authors.affiliation: Georgetown University, Department of Chemistry, Box 571227, Washington DC, 20057-1227, USA.
authors.forename: Timothy H
authors.initials: TH
authors.lastname: Warren
authors.affiliation: Organisch-Chemisches Institut, Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Gerhard
authors.initials: G
authors.lastname: Erker
keywords: CO reduction; boron; dihydrogen splitting; frustrated Lewis pairs; nitroxide radicals; phosphorus