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  Molecular and Electronic Structure of Four‐ and Five‐Coordinate Cobalt Complexes Containing Two o‐Phenylenediamine‐ or Two o‐Aminophenol‐Type Ligands at Various Oxidation Levels: An Experimental, Density Functional, and Correlated ab initio Study

Bill, E., Bothe, E., Chaudhuri, P., Chlopek, K., Herebian, D., Kokatam, S., et al. (2004). Molecular and Electronic Structure of Four‐ and Five‐Coordinate Cobalt Complexes Containing Two o‐Phenylenediamine‐ or Two o‐Aminophenol‐Type Ligands at Various Oxidation Levels: An Experimental, Density Functional, and Correlated ab initio Study. Chemistry – A European Journal, 11(1), 204-224. doi:10.1002/chem.200400850.

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 Urheber:
Bill, Eckhard1, Autor           
Bothe, Eberhard1, Autor           
Chaudhuri, Phalguni1, Autor           
Chlopek, Krzysztof1, Autor           
Herebian, Diran1, Autor           
Kokatam, Swarnalatha1, Autor           
Ray, Kallol1, Autor           
Weyhermüller, Thomas1, Autor           
Neese, Frank1, Autor           
Wieghardt, Karl1, Autor           
Affiliations:
1Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              

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Schlagwörter: ab initio calculations; cobalt; density functional calculations; nickel; radical ions
 Zusammenfassung: The bidentate ligands N‐phenyl‐o‐phenylenediamine, H2(2), or its analogue 2‐(2‐trifluoromethyl)anilino‐4,6‐di‐tert‐butylphenol, (4), react with [CoII(CH3CO2)2]⋅4H2O and triethylamine in acetonitrile in the presence of air yielding the square‐planar, four‐coordinate species [Co(2LN)2] (1) and [Co(4LO)2] (4) with an S=1/2 ground state. The corresponding nickel complexes [Ni(4LO)2] (8) and its cobaltocene reduced form [CoIII(Cp)2][Ni(4LO)2] (9) have also been synthesized. The five‐coordinate species [Co(2LN)2(tBu‐py)] (2) (S=1/2) and its one‐electron oxidized forms [Co(2LN)2(tBu‐py)](O2CCH3) (2 a) or [Co(2LN)2I] (3) with diamagnetic ground states (S=0) have been prepared, as has the species [Co(4LO)2(CH2CN)] (7). The one‐electron reduced form of 4, namely [Co(Cp)2][Co(4LO)2] (5) has been generated through the reduction of 4 with [Co(Cp)2]. Complexes 1, 2, 2 a, 3, 4, 5, 7, 8, and 9 have been characterized by X‐ray crystallography (100 K). The ligands are non‐innocent and may exist as catecholate‐like dianions (2)2−, (4)2− or π‐radical semiquinonate monoanions (2).−, (4).− or as neutral benzoquinones (2)0, (4)0; the spectroscopic oxidation states of the central metal ions vary accordingly. Electronic absorption, magnetic circular dichroism, and EPR spectroscopy, as well as variable temperature magnetic susceptibility measurements have been used to experimentally determine the electronic structures of these complexes. Density functional theoretical (DFT) and correlated ab initio calculation have been performed on the neutral and monoanionic species [Co(1LN)2]0,− in order to understand the structural and spectroscopic properties of complexes. It is shown that the corresponding nickel complexes 8 and 9 contain a low‐spin nickel(II) ion regardless of the oxidation level of the ligand, whereas for the corresponding cobalt complexes the situation is more complicated. Spectroscopic oxidation states describing a d6 (CoIII) or d7 (CoII) electron configuration cannot be unambiguously assigned.

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Sprache(n): eng - English
 Datum: 2004-08-172004-12-152004-12-17
 Publikationsstatus: Erschienen
 Seiten: 21
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1002/chem.200400850
 Art des Abschluß: -

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Titel: Chemistry – A European Journal
  Andere : Chem. – Eur. J.
  Andere : Chem. Eur. J.
Genre der Quelle: Zeitschrift
 Urheber:
Affiliations:
Ort, Verlag, Ausgabe: Weinheim : Wiley-VCH
Seiten: - Band / Heft: 11 (1) Artikelnummer: - Start- / Endseite: 204 - 224 Identifikator: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058