Taylor, Christopher G. P., Metherell, Alexander J., Argent, Stephen P., Ashour, Fatma, Williams, Nicholas H. and Ward, Michael D. (2020) Coordination cage catalysed hydrolysis of organophosphates : cavity or surface based? Chemistry – A European Journal . doi:10.1002/chem.201904708 (In Press)

PDF WRAP-coordination-cage-catalysed-hydrolysis-organophosphates-Taylor-2019.pdf - Accepted Version Embargoed item. Restricted access to Repository staff only until 27 November 2020. Contact author directly, specifying your specific needs. - Requires a PDF viewer. Download (2388Kb)

Request Changes to record.

Abstract

The hydrophobic central cavity of a water‐soluble M8L12 cubic coordination cage can accommodate a range of phospho‐diester and phospho‐triester guests such as the insecticide 'dichlorvos' (2,2‐dichlorovinyl dimethyl phosphate) and the chemical warfare agent analogue diisopropyl chlorophosphate. The accumulation of hydroxide ions around the cationic cage surface due to ion‐pairing in solution generates a high local pH around the cage, resulting in catalysed hydrolysis of the phospho‐triester guests. A series of control experiments unexpectedly demonstrates that – in marked contrast to previous cases – it is not necessary for the phospho‐triester substrates to be bound inside the cavity for catalysed hydrolysis to occur. This suggests that catalysis can occur on the exterior surface of the cage as well as the interior surface, with the exterior‐binding catalysis pathway dominating here because of the small binding constants for these phospho‐triester substrates in the cage cavity. These observations suggest that cationic but hydrophobic surfaces could act as quite general catalysts in water by bringing substrates into contact with the surface (via the hydrophobic effect) where there is also a high local concentration of anions (due to ion‐pairing / electrostatic effects).

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH):	Organophosphorus compounds , Organophosphorus compounds -- Reactivity, Catalysis
Journal or Publication Title:	Chemistry – A European Journal
Publisher:	Wiley
ISSN:	1521-3765
Official Date:	2020
Dates:	Date Event 2020 Published 27 November 2019 Available 27 November 2019 Accepted
Date of first compliant deposit:	3 December 2019
DOI:	10.1002/chem.201904708
Status:	Peer Reviewed
Publication Status:	In Press
Publisher Statement:	"This is the peer reviewed version of the following article:Taylor, C. , Metherell, A. , Argent, S. , Ashour, F. , Williams, N. and Ward, M. (2019), Coordination cage catalysed hydrolysis of organophosphates: cavity or surface based?. Chem. Eur. J., which has been published in final form at http://dx.doi.org/10.1002/chem.201904708. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions."
Access rights to Published version:	Restricted or Subscription Access
RIOXX Funder/Project Grant:	Project/Grant ID RIOXX Funder Name Funder ID MT19876 Diamond Light Source http://dx.doi.org/10.13039/100011889 P/N031555/1 [EPSRC] Engineering and Physical Sciences Research Council http://dx.doi.org/10.13039/501100000266 EP/K003224/1 [EPSRC] Engineering and Physical Sciences Research Council http://dx.doi.org/10.13039/501100000266

Request changes or add full text files to a record

Repository staff actions (login required)

View Item