Cobaltocenylidene : A Mesoionic Metalloceno Carbene, Stabilized in a Gold(III) Complex

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2018
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Vanicek, Stefan
Podewitz, Maren
Pittracher, Michael
Kopacka, Holger
Wurst, Klaus
Müller, Thomas
Liedl, Klaus R.
Bildstein, Benno
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Chemistry : a European Journal. 2018, 24(13), pp. 3165-3169. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.201800147
Zusammenfassung

Oxidative addition of cobaltoceniumdiazonium bis(hexafluoridophosphate) with (pseudo)halide aurates gave gold(III) complexes containing zwitterionic cobaltoceniumide as a ligand. Its selenium derivative, cobaltoceniumselenolate, was obtained by an electrophilic aromatic substitution reaction of iodocobaltocenium iodide with Na2Se. Spectroscopic and structural data in combination with DFT calculations showed that this cobaltocenylidene species is a mesoionic carbene quite different from common N-heterocyclic carbenes. Its ligand properties (TEP, singlet-triplet gap, nucleophilicity, π-acidity, Brønsted basicity) are in part comparable to those of cyclic (amino)(alkyl/aryl)carbenes. Electrochemistry data showed that the mesoionic cobaltoceniumides are more electron-rich than their parent ferrocenes. The reversible reduction of the tricyanido gold complex appears 50 mV negative of the cobaltocenium/cobaltocene couple, whereas that of the selenide derivative is shifted cathodically by 550 mV.

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ISO 690VANICEK, Stefan, Maren PODEWITZ, Christopher HASSENRÜCK, Michael PITTRACHER, Holger KOPACKA, Klaus WURST, Thomas MÜLLER, Klaus R. LIEDL, Rainer F. WINTER, Benno BILDSTEIN, 2018. Cobaltocenylidene : A Mesoionic Metalloceno Carbene, Stabilized in a Gold(III) Complex. In: Chemistry : a European Journal. 2018, 24(13), pp. 3165-3169. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.201800147
BibTex
@article{Vanicek2018-03-02Cobal-41711,
  year={2018},
  doi={10.1002/chem.201800147},
  title={Cobaltocenylidene : A Mesoionic Metalloceno Carbene, Stabilized in a Gold(III) Complex},
  number={13},
  volume={24},
  issn={0947-6539},
  journal={Chemistry : a European Journal},
  pages={3165--3169},
  author={Vanicek, Stefan and Podewitz, Maren and Hassenrück, Christopher and Pittracher, Michael and Kopacka, Holger and Wurst, Klaus and Müller, Thomas and Liedl, Klaus R. and Winter, Rainer F. and Bildstein, Benno}
}
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