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Zeitschrift für Physikalische Chemie

International journal of research in physical chemistry and chemical physics

Editor-in-Chief: Rademann, Klaus

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Volume 232, Issue 5-6


Characterization of Trinuclear Oxo Bridged Cobalt Complexes in Isolation

Johannes Lang
  • Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universität Kaiserslautern, 67663 Kaiserslautern, Germany
  • Other articles by this author:
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/ Daniela V. Fries
  • Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universität Kaiserslautern, 67663 Kaiserslautern, Germany
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Gereon Niedner-Schatteburg
  • Corresponding author
  • Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universität Kaiserslautern, 67663 Kaiserslautern, Germany
  • Email
  • Other articles by this author:
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Published Online: 2018-02-14 | DOI: https://doi.org/10.1515/zpch-2017-1046


This study elucidates molecular structures, fragmentation pathways and relative stabilities of isolated trinuclear oxo bridged cobalt complexes of the structural type [Co3O(OAc)6(Py)n]+ (OAc=acetate, Py=pyridine, n=0, 1, 2, 3). We present infrared multiple photon dissociation (IR-MPD) spectra in combination with quantum chemical calculations. They indicate that the coordination of axial pyridine ligands to the [Co3O(OAc)6]+ subunit disturbs the triangular geometry of the Co3O core. [Co3O(OAc)6]+ exhibits a nearly equilateral triangular Co3O core geometry. The coordination of one or two pyridine ligands disturbs this arrangement resulting in isosceles triangular Co3O core geometries (in the cases of n=1 and 2). Coordination of three pyridine ligands (n=3) results in an equilateral triangular Co3O core geometry as in the case of n=0. Collision induced dissociation (CID) studies reveal that the complexes undergo a consecutive elimination of pyridine and acetate ligands with increasing excitation energy. Relative stabilities of the complexes decrease with the number of coordinated pyridine ligands. The presented results help to gain a fundamental insight into the molecular structure of trinuclear oxo bridged cobalt complexes void of any external effects such as crystal packing or solvation.

This article offers supplementary material which is provided at the end of the article.

Keywords: DFT modeling; spectroscopy


  • Dedicated to: Eckart Rühl on the occasion of his 60th birthday.


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About the article

Received: 2017-10-12

Accepted: 2018-01-21

Published Online: 2018-02-14

Published in Print: 2018-05-24

Citation Information: Zeitschrift für Physikalische Chemie, Volume 232, Issue 5-6, Pages 649–669, ISSN (Online) 2196-7156, ISSN (Print) 0942-9352, DOI: https://doi.org/10.1515/zpch-2017-1046.

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