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Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Ambiguous reactivity of Li/Cl phosphinidenoid complexes under redox conditions - a novel dichotomy in phosphorus
Cristina Murcia García1, Antonio Bauzá, Gregor Schnakenburg
1Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn, Gerhard-Domagk-Straße 1, D-53121 Bonn, Germany. r.streubel@uni-bonn.de.
Abstract:
A novel ambiguous reactivity of Li/Cl phosphinidenoid complexes under redox conditions is described. The outcome of the reaction with hexafluoroacetone is highly dependent on the P-substituent as fluoride substitution occurred in the case of R = CPh3 and C5Me5via a radical pathway, whereas for R = CH(SiMe3)2 a complex having a novel 1,2-diol-type P-ligand was obtained via a closed-shell pathway. DFT calculations reveal a new SET pathway starting with a noncovalent π-hole complex between the phosphinidenoid anion and hexafluoroacetone followed by an elimination of LiF. The second, closed-shell reaction course is strongly influenced by a noncovalent OSi interaction established after the initial nucleophilic attack.
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