Tuning Coordination Environments Through Ligand Redox Chemistry: the Thiol–Disulfide Reaction

Edwin C. Constable; Catherine E. Housecroft; Markus Neuburger; Jason R. Price; Jennifer A. Zampese

doi:10.1071/CH10105

RESEARCH ARTICLE

Tuning Coordination Environments Through Ligand Redox Chemistry: the Thiol–Disulfide Reaction

Edwin C. Constable ^A , Catherine E. Housecroft ^A ^B , Markus Neuburger ^A , Jason R. Price ^A and Jennifer A. Zampese ^A

+ Author Affiliations

- Author Affiliations

^A Department of Chemistry, University of Basel, Spitalstrasse 51, CH–4056 Basel, Switzerland.

^B Corresponding author. Email: catherine.housecroft@unibas.ch

Australian Journal of Chemistry 63(9) 1334-1341 https://doi.org/10.1071/CH10105
Submitted: 3 March 2010 Accepted: 19 May 2010 Published: 9 September 2010

Abstract

Oxidative coupling of 6-(pyridin-2-yl)pyridine-2(1H)-thione yields 1,2-bis(2,2′-bipyridin-6-yl)disulfide (4), which can act as a bis(chelate) to a single zinc(ii) centre. The effects on the solid-state structure of introducing a methyl substituent into each 6-position of 4 have been examined. Ligand 4 functions as a bridging ligand in [Cu₂(μ-4)(μ-6)]⁴⁺ in which ligand 6 is 1,2-bis(2,2′:6′,2″-terpyridin-4′-yl)disulfide; [Cu₂(μ-4)(μ-6)]⁴⁺ self-assembles from the components according to the preference shown by copper(ii) for a five-coordinate {Cu(bpy)(tpy)} environment. Reaction of 4 with [Cu(NCMe)₄][PF₆] leads to a product, tentatively formulated as {[Cu(4)][PF₆]}_n, which, in air, undergoes oxidation of both copper and ligand to yield [Cu(5)₂] (H5 = 2,2′-bipyridine-6-sulfonic acid), the solid state structure of which is presented.

Acknowledgements

We thank the Swiss National Science Foundation and the University of Basel for financial support.

References

Tuning Coordination Environments Through Ligand Redox Chemistry: the Thiol–Disulfide Reaction

Abstract

Acknowledgements

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