Issue 4, 2011

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

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
21 Oct 2010
Accepted
29 Nov 2010
First published
05 Jan 2011

Chem. Sci., 2011,2, 696-700

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

A. M. Belenguer, T. Friščić, G. M. Day and J. K. M. Sanders, Chem. Sci., 2011, 2, 696 DOI: 10.1039/C0SC00533A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements