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Cobalt(II)/(III) Complexes Containingo-Iminothiobenzosemiquinonato(1−) ando-Iminobenzosemiquinonato(1−) π-Radical Ligands

2002; Wiley; Volume: 2002; Issue: 8 Linguagem: Inglês

10.1002/1099-0682(200208)2002

1099-0682

Diran Herebıan, Prasanta Ghosh, Hyungphil Chun, E. Bothe, Thomas Weyhermüller, Karl Wieghardt,

Metal complexes synthesis and properties

European Journal of Inorganic ChemistryVolume 2002, Issue 8 p. 1957-1967 Full Paper Cobalt(II)/(III) Complexes Containing o-Iminothiobenzosemiquinonato(1−) and o-Iminobenzosemiquinonato(1−) π-Radical Ligands Diran Herebian, Diran Herebian Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34−36, 45470 Mülheim an der Ruhr, GermanySearch for more papers by this authorPrasanta Ghosh, Prasanta Ghosh Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34−36, 45470 Mülheim an der Ruhr, GermanySearch for more papers by this authorHyungphil Chun, Hyungphil Chun Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34−36, 45470 Mülheim an der Ruhr, GermanySearch for more papers by this authorEberhard Bothe, Eberhard Bothe Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34−36, 45470 Mülheim an der Ruhr, GermanySearch for more papers by this authorThomas Weyhermüller, Thomas Weyhermüller Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34−36, 45470 Mülheim an der Ruhr, GermanySearch for more papers by this authorKarl Wieghardt, Karl Wieghardt Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34−36, 45470 Mülheim an der Ruhr, GermanySearch for more papers by this author Diran Herebian, Diran Herebian Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34−36, 45470 Mülheim an der Ruhr, GermanySearch for more papers by this authorPrasanta Ghosh, Prasanta Ghosh Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34−36, 45470 Mülheim an der Ruhr, GermanySearch for more papers by this authorHyungphil Chun, Hyungphil Chun Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34−36, 45470 Mülheim an der Ruhr, GermanySearch for more papers by this authorEberhard Bothe, Eberhard Bothe Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34−36, 45470 Mülheim an der Ruhr, GermanySearch for more papers by this authorThomas Weyhermüller, Thomas Weyhermüller Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34−36, 45470 Mülheim an der Ruhr, GermanySearch for more papers by this authorKarl Wieghardt, Karl Wieghardt Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34−36, 45470 Mülheim an der Ruhr, GermanySearch for more papers by this author First published: 02 July 2002 https://doi.org/10.1002/1099-0682(200208)2002:8 3.0.CO;2-ACitations: 64Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Abstract The coordination chemistry of 6-amino-2,4-di-tert-butylthiophenol (H[LSAP]) and of 2-anilino-4,6-di-tert-butylphenol (H[LOAP]) with cobalt(II) ions was investigated in the presence and absence of dioxygen. It was shown that both compounds were redox-non-innocent ligands, existing in different protonation and oxidation levels as: (i) o-aminophenolates(1−) [(LXAP)1−], (ii) o-imidophenolates(2−) [(LXIP)2−], and (iii) one-electron oxidized forms o-iminobenzosemiquinonates(1−) [(LXISQ)1−], which are π-radicals (X = S, O for the sulfur or oxygen derivative). The following complexes were synthesized: [CoII(LSAP)2]2 (1), [CoII(LSISQ)2]2·0.5n-hexane (2·0.5n-hexane), [CoIIII(LSISQ)2] (3), [CoIIII(LOISQ)2] (4), and [CoIIICl(LOISQ)2] (5). The compounds 2·0.5n-hexane, 4, and 5 were structurally characterized by X-ray crystallography. It was shown that the different protonation and oxidation levels of the ligands could readily be identified by X-ray crystallography. Complex 2 could be reversibly oxidized and reduced electrochemically, yielding a monocation and a monoanion, respectively. It was shown that these processes were metal-centered ([CoIII(LSISQ)2]+, [CoII(LSISQ)2], and [CoI(LSISQ)2]−). The electronic structures were elucidated by UV/Vis and EPR spectroscopy and magnetochemistry. Complexes 3, 4, and 5 were shown to be singlet diradicals. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002) Citing Literature Volume2002, Issue8August 2002Pages 1957-1967 RelatedInformation