Filters

20202

More filters

20212
Reset filters

Settings

Author: Oberem, Elisabeth × End date: 2024 × Start date: 2020 × DDC: 540 × DDC: 660 × WGL Institute: LIKAT ×

Search Results

Now showing 1 - 2 of 2
  • Thumbnail Image
    Item
    Metal/Metal Redox Isomerism Governed by Configuration
    (Weinheim : Wiley-VCH, 2020) Ludwig, Stephan; Helmdach, Kai; Hettenschmidt, Mareike; Oberem, Elisabeth; Rabeah, Jabor; Villinger, Alexander; Ludwig, Ralf; Seidel, Wolfram W.
    A pair of diastereomeric dinuclear complexes, [Tp′(CO)BrW{μ-η2-C,C′-κ2-S,P-C2(PPh2)S}Ru(η5-C5H5)(PPh3)], in which W and Ru are bridged by a phosphinyl(thiolato)alkyne in a side-on carbon P,S-chelate coordination mode, were synthesized, separated and fully characterized. Even though the isomers are similar in their spectroscopic properties and redox potentials, the like-isomer is oxidized at W while the unlike-isomer is oxidized at Ru, which is proven by IR, NIR and EPR-spectroscopy supported by spectro-electrochemistry and computational methods. The second oxidation of the complexes was shown to take place at the metal left unaffected in the first redox step. Finally, the tipping point could be realized in the unlike isomer of the electronically tuned thiophenolate congener [Tp′(CO)(PhS)W{μ-η2-C,C′-κ2-S,P-C2(PPh2)S}Ru(η5-C5H5)-(PPh3)], in which valence trapped WIII/RuII and WII/RuIII cationic species are at equilibrium. © 2020 The Authors. Published by Wiley-VCH GmbH
  • Thumbnail Image
    Item
    Facile Synthesis of a Stable Side-on Phosphinyne Complex by Redox Driven Intramolecular Cyclisation
    (Weinheim : Wiley-VCH, 2020) Lange, Helge; Schröder, Henning; Oberem, Elisabeth; Villinger, Alexander; Rabeah, Jabor; Ludwig, Ralf; Neymeyr, Klaus; Seidel, Wolfram W.
    Alkyne complexes with vicinal substitution by a Lewis acid and a Lewis base at the coordinated alkyne are prospective frustrated Lewis pairs exhibiting a particular mutual distance and, hence, a specific activation potential. In this contribution, investigations on the generation of a WII alkyne complex bearing a phosphine as Lewis base and a carbenium group as Lewis acid are presented. Independently on potential substrates added, an intramolecular cyclisation product was always isolated. A subsequent deprotonation step led to an unprecedented side-on λ5-phosphinyne complex, which is interpreted as highly zwitterionic according to visible absorption spectroscopy supported by TD-DFT. Low-temperature 31P NMR and EPR spectroscopic measurements combined with time-dependent IR-spectroscopic monitoring provided insights in the mechanism of the cyclisation reaction. Decomposition of the multicomponent IR spectra by multivariate curve resolution and a kinetic hard-modelling approach allowed the derivation of kinetic parameters. Assignment of the individual IR spectra to potential intermediates was provided by DFT calculations. © 2020 The Authors. Published by Wiley-VCH GmbH