Electron transfer in dinuclear cobalt complexes with ''non-innocent'' bridging ligands
- Publication type:
- Journal article
- Metadata:
-
- Autoren
- K Heinze
- G Huttner
- L Zsolnai
- A Jacobi
- P Schober
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:A1997XJ95900010&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1002/chem.19970030513
- Externe Identifier
- Clarivate Analytics Document Solution ID: XJ959
- ISSN
- 0947-6539
- Ausgabe der Veröffentlichung
- 5
- Zeitschrift
- CHEMISTRY-A EUROPEAN JOURNAL
- Schlüsselwörter
- bridging ligands
- charge transfer
- cobalt
- quinones
- tripodal ligands
- Paginierung
- 732 - 743
- Datum der Veröffentlichung
- 1997
- Status
- Published
- Titel
- Electron transfer in dinuclear cobalt complexes with ''non-innocent'' bridging ligands
- Sub types
- Article
- Proceedings Paper
- Ausgabe der Zeitschrift
- 3
Data source: Web of Science (Lite)
- Other metadata sources:
-
- Abstract
- <jats:title>Abstract</jats:title><jats:p>Reaction of tripod cobalt(II) templates [{CH<jats:sub>3</jats:sub>C(CH<jats:sub>2</jats:sub>PAr<jats:sub>2</jats:sub>)<jats:sub>3</jats:sub>}Co<jats:sup>II</jats:sup>] with potentially bridging ligands L generates the dinuclear compounds [(tripod)‐Co‐L‐Co(tripod)]<jats:sup>2+</jats:sup>. With L = oxalate (C<jats:sub>2</jats:sub>O<jats:sup>2‐</jats:sup><jats:sub>4</jats:sub>) a biscobalt(II) complex (<jats:bold>1</jats:bold>) is formed, while with L = C<jats:sub>6</jats:sub>H<jats:sub>2</jats:sub>O<jats:sup>2‐</jats:sup><jats:sub>4</jats:sub>, the dianion derived from 2,5‐dihydroxy‐1,4=benzoquinone (anilic acid), two‐electron transfer within the dimetallic unit occurs and a biscobalt(III) charge distribution results (<jats:bold>2a</jats:bold>), as shown by X‐ray structural analyses of <jats:bold>1</jats:bold> and <jats:bold>2a</jats:bold>, NMR spectroscopy, and theoretical investigations by the INDO method. Complex <jats:bold>2a</jats:bold> exhibits an unusually intense, low‐energy absorption in its electronic spectrum; this is explained with a simple MO model. One‐electron reduction of <jats:bold>2a</jats:bold> generates the corresponding mixed‐valence complex, which is highly stabilised through extensive electron delocalisation. Substituents at the 3,6 positions of the bridging ligand (Cl, Br, I, NO<jats:sub>2</jats:sub>, Me, <jats:italic>i</jats:italic>Pr, Ph; <jats:bold>2b‐h</jats:bold>) as well as alkyl substitution at the aromatic rings of the tripod ligands (<jats:bold>3, 4</jats:bold>) influence the optical and electrochemical properties consistent with the proposed model of charge distribution. Formal replacement of one [(tripod)Co<jats:sup>III</jats:sup>]<jats:sup>3+</jats:sup> moiety by [CH<jats:sub>2</jats:sub>]<jats:sup>2+</jats:sup> leads to the mononuclear complex <jats:bold>6</jats:bold>, which is shown to be a typical [(tripod)Co<jats:sup>III</jats:sup>=(catecholato)]<jats:sup>+</jats:sup> complex. Therefore the substantially different optical and electrochemical properties of the dinuclear complexes with respect to those of <jats:bold>6</jats:bold> result from strong metal‐metal interactions mediated by the bridging ligand.</jats:p>
- Autoren
- Katja Heinze
- Gottfried Huttner
- Laszlo Zsolnai
- Albrecht Jacobi
- Peter Schober
- DOI
- 10.1002/chem.19970030513
- eISSN
- 1521-3765
- ISSN
- 0947-6539
- Ausgabe der Veröffentlichung
- 5
- Zeitschrift
- Chemistry – A European Journal
- Sprache
- en
- Online publication date
- 2006
- Paginierung
- 732 - 743
- Datum der Veröffentlichung
- 1997
- Status
- Published
- Herausgeber
- Wiley
- Herausgeber URL
- http://dx.doi.org/10.1002/chem.19970030513
- Datum der Datenerfassung
- 2023
- Titel
- Electron Transfer in Dinuclear Cobalt Complexes with “Non‐innocent” Bridging Ligands
- Ausgabe der Zeitschrift
- 3
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