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@PHDTHESIS{Hppe:973774,
      author       = {Hüppe, Henrika Maria},
      othercontributors = {Herres-Pawlis, Sonja and Oppel, Iris Marga},
      title        = {{C}oordination chemistry of bioinspired iron complexes with
                      tri- and tetradentate ligands : solid state structures,
                      solution behaviour and reactivity},
      school       = {RWTH Aachen University},
      type         = {Dissertation},
      address      = {Aachen},
      publisher    = {RWTH Aachen University},
      reportid     = {RWTH-2023-10995},
      pages        = {1 Online-Ressource : Illustrationen},
      year         = {2023},
      note         = {Veröffentlicht auf dem Publikationsserver der RWTH Aachen
                      University 2024; Dissertation, RWTH Aachen University, 2023},
      abstract     = {Inspired by nature, biomimetic iron complexes can be used
                      to act as catalysts in selective oxidation reactions. In
                      this process, high-valent oxo species of the iron complexes
                      are passed through. Besides the ligand design for such iron
                      complexes, the structure of the precursor complexes and the
                      coordination chemical behaviour in solution are key to the
                      high-valent iron-oxo species and to investigate their
                      catalytic activity. In this work, tri- and tetradentate
                      ligands with N- and O-donors were synthesised and
                      investigated. For a bis(pyrazolyl)ethanol ligand, a
                      bisfacial coordination of iron with a {N3}-coordination of
                      the ligand was found. The investigated tetradentate ligands
                      (MeC(Py)2Phen, MeC(Py)2PicMe and NQu3) with {N4}- or
                      {N3O}-donor set always leave two cis-positioned coordination
                      sites for labile co-ligands in an octahedral coordination
                      environment. These are particularly important for catalytic
                      oxidation reactions with high-valent iron-oxo intermediates.
                      For all three tetradentate ligands, a [Fe(IV)L=O]2+ species
                      could be detected by mass spectrometry. UV/Vis spectroscopic
                      investigations also show typical iron-oxo bands. For
                      complexes with the ligand MeC(Py)2Phen, the catalytic C-H
                      bond oxidation could also be successfully investigated. The
                      structure of the corresponding precursor complexes was
                      investigated in the solid state and in solution. The main
                      focus was on the co-ligand competition of triflate and
                      acetonitrile. While different species were observed in the
                      solid state, all results in solution suggest that
                      acetonitrile is coordinating when used as a solvent.
                      Furthermore, spin crossover behaviour in solution was
                      observed for complexes with ligands MeC(Py)2PicMe and NQu3
                      in acetonitrile. A large number of potential precursor
                      complexes with (weakly) coordinating anions could be
                      structurally characterised by single crystal X-ray
                      diffraction. Selected substances were also investigated with
                      magnetometry or Mößbauer spectroscopy. UV/Vis
                      spectroscopy, NMR spectroscopy, magnetometry or Mößbauer
                      spectroscopy were used for coordination chemical
                      investigations in solution. The low-spin complex
                      [Fe(MeC(Py)2Phen)(MeCN)2](OTf)2 was investigated for
                      short-lived excited states by femtosecond X-ray emission
                      spectroscopy and compared with the photophysical properties
                      of a bisfacial iron(II) complex of a
                      bis(pyrazolyl)pyridinylmethane ligand. Both show similar
                      photophysical behaviour to that of the well-studied iron(II)
                      bipyridinyl complex.},
      cin          = {151910 / 150000},
      ddc          = {540},
      cid          = {$I:(DE-82)151910_20150909$ / $I:(DE-82)150000_20140620$},
      typ          = {PUB:(DE-HGF)11},
      doi          = {10.18154/RWTH-2023-10995},
      url          = {https://publications.rwth-aachen.de/record/973774},
}