NDLI: Ambiguous reactivity of Li/Cl phosphinidenoid complexes under redox conditions – a novel dichotomy in phosphorus chemistry

Content Provider	Royal Society of Chemistry (RSC)
Author	García, Cristina Murcia Schnakenburg, Gregor Bauzá, Antonio Frontera, Antonio Streubel, Rainer
Copyright Year	2017
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 O⋯Si interaction established after the initial nucleophilic attack.
Starting Page	933
Ending Page	936
Page Count	4
File Format	HTM / HTML PDF
ISSN	13597345
Volume Number	53
Issue Number	5
Journal	Chemical Communications
DOI	10.1039/c6cc09620d
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Fluorine Redox Ion Hexafluoroacetone
Content Type	Text
Resource Type	Article
Subject	Ceramics and Composites Chemistry Surfaces, Coatings and Films Materials Chemistry Metals and Alloys Electronic, Optical and Magnetic Materials Catalysis

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Ambiguous reactivity of Li/Cl phosphinidenoid complexes under redox conditions – a novel dichotomy in phosphorus chemistry