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  The Electronic Structure of the Isoelectronic, Square-Planar Complexes [FeII(L)2]2- and [CoIII(LBu)2]- (L2- and (LBu)2- = Benzene-1,2-dithiolates):  An Experimental and Density Functional Theoretical Study

Ray, K., Begum, A., Weyhermüller, T., Piligkos, S., van Slageren, J., Neese, F., et al. (2005). The Electronic Structure of the Isoelectronic, Square-Planar Complexes [FeII(L)2]2- and [CoIII(LBu)2]- (L2- and (LBu)2- = Benzene-1,2-dithiolates):  An Experimental and Density Functional Theoretical Study. Journal of the American Chemical Society, 127(12), 4403-4415. doi:10.1021/ja042803i.

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Ray, Kallol1, Author              
Begum, Ameerunisha1, Author              
Weyhermüller, Thomas1, Author              
Piligkos, Stergios1, Author              
van Slageren, Joris2, Author
Neese, Frank1, Author              
Wieghardt, Karl1, Author              
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1Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              
21.Physikalisches Institut, Universität Stuttgart , Pfaffenwaldring 57, D-70550 Stuttgart, Germany, ou_persistent22              

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 Abstract: The electronic structures of two formally isoelectronic transition-metal dithiolato complexes [Fe(L)2]2- (1) and [Co(LBu)2]1- (2) both possessing a spin triplet ground state (St = 1) have been investigated by various spectroscopic and density functional methods; H2LBu represents the pro-ligand 3,5-di-tert-butylbenzene-1,2-dithiol and H2L is the corresponding unsubstituted benzene-1,2-dithiol. An axial zero-field splitting (D) of +32 cm-1 for 2 has been measured independently by SQUID magnetometry, far-infrared absorption, and variable-temperature and variable-field (VTVH) magnetic circular dichroism spectroscopies. A similar D value of +28 cm-1 is obtained for 1 on the basis of VTVH SQUID measurements. The absorption spectra of 1 and 2 are found, however, to be very different. Complex 1 is light yellow in color with no intense transition in the visible region, whereas 2 is deep blue. DFT calculations establish that the electronic structures of the [Fe(L)2]2- and [Co(L)2]1- anions are very different and explain the observed differences in their absorption spectra. On the basis of these spectroscopic and theoretical analyses, 1 is best described as containing an intermediate spin Fe(II) ion, whereas for the corresponding cobalt complex, oxidation states describing a d6 (CoIII) or d7 (CoII) electron configuration cannot be unambiguously assigned. The physical origin of the large zero-field splitting in both 1 and 2 is found to be due to the presence of low-energy spin-conserved d−d excitations which lead to a large Dzz through efficient spin−orbit coupling. Differential covalency effects appear to be of limited importance for this property.

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Language(s): eng - English
 Dates: 2004-11-302005-03-01
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ja042803i
 Degree: -

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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 127 (12) Sequence Number: - Start / End Page: 4403 - 4415 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870