Issue 6, 2002
From the journal:

Journal of the Chemical Society, Perkin Transactions 2

Sandmeyer reactions. Part 6.1 A mechanistic investigation into the reduction and ligand transfer steps of Sandmeyer cyanation

Peter Hanson,*a   Simon C. Rowell,a   Alec B. Taylor,a   Paul H. Waltona  and  Allan W. Timmsb  

* Corresponding authors

a Department of Chemistry, University of York, Heslington, UK

b Great Lakes Fine Chemicals Ltd., Halebank, Widnes, UK

Abstract

For Sandmeyer cyanation at 298 K in 50% v/v aqueous acetonitrile buffered at pH 8, absolute rate constants have been obtained for the reduction of 4-methoxybenzenediazonium tetrafluoroborate by the cyanocuprate(I) anions CuI(CN)43−, CuI(NCMe)(CN)32− and CuI(NCMe)2(CN)2− as (0.50 ± 0.05), (0.12 ± 0.03) and 0.0 dm3 mol−1 s−1, respectively. The relative reactivity of the two reactive cyanocuprates reflects the estimated difference in their standard reduction potentials. Ligand transfer to the aryl radical from the cyanocuprate(II) anions produced in the reaction occurs within the solvent cage. By use of radical clocks, first order rate constants of the order of 1 × 108 s−1 for ligand transfer between the caged reactants can be evaluated although the transfer rate may vary from one aryl radical to another. No difference was discerned in ligand transferring reactivity between the two cyanocuprate(II) complexes involved.

Graphical abstract: Sandmeyer reactions. Part 6.1 A mechanistic investigation into the reduction and ligand transfer steps of Sandmeyer cyanation

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Article information

DOI
https://doi.org/10.1039/B200747A
Article type
Paper
Submitted
21 Jan 2002
Accepted
21 Mar 2002
First published
19 Apr 2002

J. Chem. Soc., Perkin Trans. 2, 2002, 1126-1134

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Sandmeyer reactions. Part 6. A mechanistic investigation into the reduction and ligand transfer steps of Sandmeyer cyanation

P. Hanson, S. C. Rowell, A. B. Taylor, P. H. Walton and A. W. Timms, J. Chem. Soc., Perkin Trans. 2, 2002, 1126 DOI: 10.1039/B200747A

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