Cu(II)‐catalyzed hydrolysis of tris‐2‐pyridyl phosphate assisted by sodium dodecyl sulfate micelles

Hydrolysis of the phosphate triester tris‐2‐pyridyl phosphate is catalyzed upon complexation with Cu2+, with enhancements of the order of 107‐fold in comparison to the spontaneous hydrolysis of the substrate. Experimental and theoretical results suggest that Cu2+ most probably coordinates to the nit...

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Bibliographic Details
Published in:Journal of physical organic chemistry 2019-01, Vol.32 (1), p.n/a
Main Authors: Wanderlind, Eduardo H., Bittencourt, Catiunaiara R., Manfredi, Alex M., Gerola, Adriana P., Souza, Bruno S., Fiedler, Haidi D., Nome, Faruk
Format: Article
Language:English
Subjects:
Complexation
Copper
copper catalysis
Hydrolysis
metal ion catalysis
Metallography
Micelles
Nitrogen atoms
phosphate transfer
phosphotriester
Sodium dodecyl sulfate
Substrates
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Summary:Hydrolysis of the phosphate triester tris‐2‐pyridyl phosphate is catalyzed upon complexation with Cu2+, with enhancements of the order of 107‐fold in comparison to the spontaneous hydrolysis of the substrate. Experimental and theoretical results suggest that Cu2+ most probably coordinates to the nitrogen atoms of two of the pyridyl substituents disposing a metallo‐bound water or hydroxo ligand at appropriate distance for intramolecular attack on phosphorus. Micelles of the anionic sodium dodecyl sulfate remarkably accelerate the reactions, acting as nanoreactors that concentrate in the micellar microenvironment both the hydrophobic substrate and the positively charged metal ion, favoring complexation between tris‐2‐pyridyl phosphate and Cu2+. Complexation between Cu2+ and tris‐2‐pyridyl phosphate catalyzes the phosphate hydrolysis, most probably trough intramolecular nucleophilic attack of a water ligand on phosphorus. Micelles of sodium dodecyl sulfate favor the reaction, allowing for high local concentrations of Cu2+ in the micellar environment.
ISSN:0894-3230
1099-1395
DOI:10.1002/poc.3837