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Coordination cage catalysed hydrolysis of organophosphates : cavity or surface based?
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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, 26 (14). pp. 3065-3073. doi:10.1002/chem.201904708
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Official URL: http://dx.doi.org/10.1002/chem.201904708
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 | ||||||||||||
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| 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: | 9 March 2020 | ||||||||||||
| Dates: |
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| Volume: | 26 | ||||||||||||
| Number: | 14 | ||||||||||||
| Page Range: | pp. 3065-3073 | ||||||||||||
| DOI: | 10.1002/chem.201904708 | ||||||||||||
| Status: | Peer Reviewed | ||||||||||||
| Publication Status: | Published | ||||||||||||
| 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: |
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