The Chemistry of a Non-Interacting Vicinal Frustrated Phosphane/Borane Lewis Pair.
Chemistry
; 23(25): 6056-6068, 2017 May 02.
Article
em En
| MEDLINE
| ID: mdl-27925311
ABSTRACT
The dimesitylphosphinocyclopentene/HB(C6 F5 )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(C6 F5 )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.
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01-internacional
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MEDLINE
Idioma:
En
Ano de publicação:
2017
Tipo de documento:
Article