A Tautomeric [lamda]3/[lambda]5-phosphane pair and its ambiphilic reactivity

• Verfasst von: Mörsdorf, Jean-Marc [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Verfasst von: Ballmann, Joachim [VerfasserIn]
• Titel: A Tautomeric [lamda]3/[lambda]5-phosphane pair and its ambiphilic reactivity
• Verf.angabe: Jean-Marc Mörsdorf, Hubert Wadepohl, and Joachim Ballmann
• E-Jahr: 2019
• Jahr: February 19, 2019
• Umfang: 7 S.
• Fussnoten: Gesehen am 02.05.2019
• Titel Quelle: Enthalten in: Inorganic chemistry
• Ort Quelle: Washington, DC : American Chemical Society, 1962
• Jahr Quelle: 2019
• Band/Heft Quelle: 58(2019), 5, Seite 3502-3508
• ISSN Quelle: 1520-510X
• DOI: doi:10.1021/acs.inorgchem.9b00076
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1664485546

Abstract

The central phosphorus atom of a novel hydroxyl-functionalized triarylphosphane was shown to reversibly insert into one of the molecule’s O-H bonds, which forms the basis for a tautomeric λ3/λ5-phosphane equilibrium. For the first time, this equilibrium was detected for a λ3-triarylphosphane and the underlying dynamic process was elucidated by NMR spectroscopy. On the basis of reactivity studies, a nucleophilic character was assigned to the minor species present in solution, the λ3-phosphane. Upon methylation, for example, the λ3-form was selectively removed from the equilibrium and converted to the corresponding phosphonium salt. However, upon generation of an alkoxide via proton abstraction, the electrophilic character of the λ5-phosphane in the equilibrium became evident since the alkoxide was found to attack the molecule’s phosphorus atom. This intramolecular reaction led to the selective formation of a new anionic λ6-hydridospirophosphane.