Tetragonal phosphorus() cations as tunable and robust catalytic Lewis acids

The synthesis and catalytic reactivity of a class of water-tolerant cationic phosphorus-based Lewis acids is reported. Corrole-based phosphorus( v ) cations of the type [ArP(cor)][B(C 6 F 5 ) 4 ] (Ar = C 6 H 5 , 3,5-(CF 3 ) 2 C 6 H 3 ; cor = 5,10,15-(C 6 H 5 ) 3 corrolato 3− , 5,10,15-(C 6 F 5 ) 3 c...

Full description

Saved in:
Bibliographic Details
Published in:Chemical science (Cambridge) 2019-08, Vol.1 (3), p.7177-7182
Main Authors: Gilhula, James C, Radosevich, Alexander T
Format: Article
Language:English
Subjects:
Absorption spectra
Alcohols
Basal plane
Carbohydrates
Carbonyls
Catalysis
Cations
Chemical synthesis
Crystallography
Deoxygenation
Hydrogen bonds
Hydrosilylation
Lewis acid
NMR
Nuclear magnetic resonance
Phosphorus
Spectrophotometry
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The synthesis and catalytic reactivity of a class of water-tolerant cationic phosphorus-based Lewis acids is reported. Corrole-based phosphorus( v ) cations of the type [ArP(cor)][B(C 6 F 5 ) 4 ] (Ar = C 6 H 5 , 3,5-(CF 3 ) 2 C 6 H 3 ; cor = 5,10,15-(C 6 H 5 ) 3 corrolato 3− , 5,10,15-(C 6 F 5 ) 3 corrolato 3− ) were synthesized and characterized by NMR and X-ray diffraction. The visible electronic absorption spectra of these cationic phosphacorroles depend strongly on the coordination environment at phosphorus, and their Lewis acidities are quantified by spectrophotometric titrations. DFT analyses establish that the character of the P-acceptor orbital comprises P-N antibonding interactions in the basal plane of the phosphacorrole. Consequently, the cationic phosphacorroles display unprecedented stability to water and alcohols while remaining highly active and robust Lewis acid catalysts for carbonyl hydrosilylation, C sp 3 -H bond functionalization, and carbohydrate deoxygenation reactions. The synthesis and catalytic reactivity of a class of water-tolerant cationic phosphorus-based Lewis acids is reported.
ISSN:2041-6520
2041-6539
DOI:10.1039/c9sc02463h