The first Thioallenylidene Complexes from Ruthenium-Butatrienylidene Intermediates

Winter, Rainer F.

The first Thioallenylidene Complexes from Ruthenium-Butatrienylidene Intermediates

Dateien

Winter.pdfGröße: 3.23 MBDownloads: 313

Datum

1999

Open Access-Veröffentlichung

Open Access Green

Sammlungen

Chemie

Publikationstyp

Zeitschriftenartikel

Publikationsstatus

Published

Erschienen in

European Journal of Inorganic Chemistry. 1999, 1999(12), pp. 2121-2126. ISSN 1434-1948. Available under: doi: 10.1002/(SICI)1099-0682(199912)1999:12<2121::AID-EJIC2121>3.0.CO;2-M

Zusammenfassung

Ruthenium-butatrienylidene cations trans-[Cl(L2)2Ru=C=C=C=CH2]+ are key intermediates in the synthesis of the first thioallenylidene complexes trans-[Cl(L2)2Ru=C=C=C(SR)R′]+ (L2 = dppm, R = Et, R′ = Me: 3a, L2 = dppm, R = Me, R′ = C4H7: 3b, L2 = dppe, R = C3H5, R′ = C4H7: 3c). Spectroscopic and electrochemical data for 3a–c are presented and are compared with those of their aminoallenylidene analogues. Aminoallenylidene complexes are best represented by the iminiumalkynyl resonance form, while a true cumulene description is much more appropriate for thioallenylidene complexes 3a–c. Based on a combination of spectroscopic and electrochemical data, we present evidence that the NMR shifts of the carbon atoms of the unsaturated ligand in these allenylidene complexes are correlated to the HOMO–LUMO gap. In situ EPR-, UV/Vis-, and IR-spectro-electrochemistry reveals that the one-electron oxidation occurs at the metal center, while reduction occurs at the carbon–heteroatom terminus.

Fachgebiet (DDC)

540 Chemie

Zitieren

ISO 690

WINTER, Rainer F., 1999. The first Thioallenylidene Complexes from Ruthenium-Butatrienylidene Intermediates. In: European Journal of Inorganic Chemistry. 1999, 1999(12), pp. 2121-2126. ISSN 1434-1948. Available under: doi: 10.1002/(SICI)1099-0682(199912)1999:12<2121::AID-EJIC2121>3.0.CO;2-M

BibTex

@article{Winter1999first-13856,
  year={1999},
  doi={10.1002/(SICI)1099-0682(199912)1999:12<2121::AID-EJIC2121>3.0.CO;2-M},
  title={The first Thioallenylidene Complexes from Ruthenium-Butatrienylidene Intermediates},
  number={12},
  volume={1999},
  issn={1434-1948},
  journal={European Journal of Inorganic Chemistry},
  pages={2121--2126},
  author={Winter, Rainer F.}
}

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