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Solid-state dynamic combinatorial chemistry: reversibility and thermodynamic product selection in covalent mechanosynthesis

Solid-state dynamic combinatorial chemistry: reversibility and thermodynamic product selection in covalent mechanosynthesis
Solid-state dynamic combinatorial chemistry: reversibility and thermodynamic product selection in covalent mechanosynthesis
We demonstrate the reversibility and thermodynamic control in covalent mechanosynthesis, by using the base-catalysed metathesis of aromatic disulfides as a model reaction. The mechanochemical formation of thermodynamic equilibrium mixtures is observed for both neat and liquid-assisted grinding methodologies. Different methodologies lead to mutually different equilibrium compositions, which also differ from those obtained by solution equilibration. The differences can be explained in terms of crystal packing effects superimposed onto the inherent reactivity of isolated molecules. Calculations indicate that the differences in relative energies of reactants and products in their respective crystal structures can bias the mechanochemical reaction equilibrium towards the complete conversion of reactants into the product, in that way opening the doors for the development of dynamic combinatorial synthesis in the solid state and for the rational design of solid-state synthesis using mechanochemistry.
1478-6524
696-700
Belenguer, Ana M.
1dded48e-9529-41a9-ae36-abc6a62063e0
Friščić, Tomislav
26e7e7b1-fc27-4731-827b-f09eadc14d14
Day, Graeme M.
e3be79ba-ad12-4461-b735-74d5c4355636
Sanders, Jeremy K. M.
6674333e-00f4-460e-ba56-f02bb8dc5911
Belenguer, Ana M.
1dded48e-9529-41a9-ae36-abc6a62063e0
Friščić, Tomislav
26e7e7b1-fc27-4731-827b-f09eadc14d14
Day, Graeme M.
e3be79ba-ad12-4461-b735-74d5c4355636
Sanders, Jeremy K. M.
6674333e-00f4-460e-ba56-f02bb8dc5911

Belenguer, Ana M., Friščić, Tomislav, Day, Graeme M. and Sanders, Jeremy K. M. (2011) Solid-state dynamic combinatorial chemistry: reversibility and thermodynamic product selection in covalent mechanosynthesis. Chemical Science, 2 (4), 696-700. (doi:10.1039/C0SC00533A).

Record type: Article

Abstract

We demonstrate the reversibility and thermodynamic control in covalent mechanosynthesis, by using the base-catalysed metathesis of aromatic disulfides as a model reaction. The mechanochemical formation of thermodynamic equilibrium mixtures is observed for both neat and liquid-assisted grinding methodologies. Different methodologies lead to mutually different equilibrium compositions, which also differ from those obtained by solution equilibration. The differences can be explained in terms of crystal packing effects superimposed onto the inherent reactivity of isolated molecules. Calculations indicate that the differences in relative energies of reactants and products in their respective crystal structures can bias the mechanochemical reaction equilibrium towards the complete conversion of reactants into the product, in that way opening the doors for the development of dynamic combinatorial synthesis in the solid state and for the rational design of solid-state synthesis using mechanochemistry.

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More information

e-pub ahead of print date: 5 January 2011
Published date: 2011
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Computational Systems Chemistry

Identifiers

Local EPrints ID: 343422
URI: https://eprints.soton.ac.uk/id/eprint/343422
ISSN: 1478-6524
PURE UUID: 24bc165e-3a42-47b5-956f-9383f068d13d
ORCID for Graeme M. Day: ORCID iD orcid.org/0000-0001-8396-2771

Catalogue record

Date deposited: 08 Oct 2012 09:12
Last modified: 06 Jun 2018 12:28

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