title: Ambiguous reactivity of Li/Cl phosphinidenoid complexes under redox conditions - a novel dichotomy in phosphorus chemistry.
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 = CPh3and C5Me5via a radical pathway, whereas for R = CH(SiMe3)2a 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.
authors.affiliation: Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn, Gerhard-Domagk-Straße 1, D-53121 Bonn, Germany. r.streubel@uni-bonn.de.
authors.forename: Cristina Murcia
authors.initials: CM
authors.lastname: García
authors.forename: Antonio
authors.initials: A
authors.lastname: Bauzá
authors.forename: Gregor
authors.initials: G
authors.lastname: Schnakenburg
authors.forename: Antonio
authors.initials: A
authors.lastname: Frontera
authors.forename: Rainer
authors.initials: R
authors.lastname: Streubel