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

ABSTRACT: Three diplatinum(II) complexes [{PtL}2(?-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 thea(4-) ligand may lead to an increased through-space interaction between the dioxolene ? systems.

SUBMITTER: Loughrey JJ

PROVIDER: S-EPMC4164269 | biostudies-literature | 2014 May

REPOSITORIES: biostudies-literature

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

Loughrey Jonathan J JJ Sproules Stephen S McInnes Eric J L EJ Hardie Michaele J MJ Halcrow Malcolm A MA

Chemistry (Weinheim an der Bergstrasse, Germany) 20140202 21

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/ ...[more]

PMID: 24488824

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