Stable mixed-valent radicals from platinum(II) complexes of a bis(dioxolene) ligand

Loughrey, J. J., Sproules, S. , McInnes, E. J.L., Hardie, M. J. and Halcrow, M. A. (2014) Stable mixed-valent radicals from platinum(II) complexes of a bis(dioxolene) ligand. Chemistry: A European Journal, 20(21), pp. 6272-6276. (doi: 10.1002/chem.201304848)

Abstract

Three diplatinum(II) complexes [{PtL}₂(μ-thea)] (H4thea=2,3,6,7-tetrahydroxy-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene) have been prepared, with diphosphine or bipyridyl “L” co-ligands. One-electron oxidation of these complexes gave radical cations containing a mixed-valent [thea ]³⁻ ligand with discrete catecholate and semiquinonate centers separated by quaternary methylene spacers. The electronic character of these radicals is near the Robin–Day class II/III border determined by UV/Vis/NIR and EPR spectroscopies. Crystal-structure determinations and a DFT calculation imply that oxidation of the thea⁴⁻ ligand may lead to an increased through-space interaction between the dioxolene π systems.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Sproules, Dr Stephen
• Authors: Loughrey, J. J., Sproules, S., McInnes, E. J.L., Hardie, M. J., and Halcrow, M. A.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Chemistry: A European Journal
• Publisher: Wiley-VCH Verlag
• ISSN: 0947-6539
• ISSN (Online): 1521-3765
• Copyright Holders: Copyright © 2014 The Authors
• First Published: First published in Chemistry: A European Journal 20(21):6272-6276
• Publisher Policy: Reproduced under a Creative Commons License