Macrocyclic dithiomaleonitriles for an efficient PdCl2 coordination
- We have synthesized a set of new unsaturated macrocyclic dithioethers with an increasing number of flexible methylene units 1-7 (Scheme 2) to investigate the correlation between the ring size of these ligands, the chelation effect and the consequences for an efficient PdCl2 coordination. The dithioethers 1-7 and the complex [PdCl2(4)]center dot CHCl3 were characterized by X-ray diffraction analysis. The crystal structures of 1-7 show that 2-7 are better preorganized chelating ligands for an exocyclic PdCl2 coordination than 1. The chelation effect of 1-7, the orientation of the sulfur atoms and the S center dot center dot center dot S donor distances, are influenced by the flexibility of the methylene units. In this series the unsaturated macrocyclic ligands 5 and 6 are the best chelating ligands for an efficient PdCl2 coordination. Comparative solvent extraction experiments with mn-12S(2)O(2) (mn = maleonitrile) reveal that the low interface activity of the new ligands reduces the extraction rate. However, a comparison withWe have synthesized a set of new unsaturated macrocyclic dithioethers with an increasing number of flexible methylene units 1-7 (Scheme 2) to investigate the correlation between the ring size of these ligands, the chelation effect and the consequences for an efficient PdCl2 coordination. The dithioethers 1-7 and the complex [PdCl2(4)]center dot CHCl3 were characterized by X-ray diffraction analysis. The crystal structures of 1-7 show that 2-7 are better preorganized chelating ligands for an exocyclic PdCl2 coordination than 1. The chelation effect of 1-7, the orientation of the sulfur atoms and the S center dot center dot center dot S donor distances, are influenced by the flexibility of the methylene units. In this series the unsaturated macrocyclic ligands 5 and 6 are the best chelating ligands for an efficient PdCl2 coordination. Comparative solvent extraction experiments with mn-12S(2)O(2) (mn = maleonitrile) reveal that the low interface activity of the new ligands reduces the extraction rate. However, a comparison with open-chain dithiomaleonitriles shows the impact of the macrocyclic effect of 4 and 5 on the extraction yield.…
Verfasserangaben: | Thomas SchwarzeORCiD, Juliane Traeger, Alexandra Kelling, Uwe SchildeORCiDGND, Hans-Jürgen HoldtORCiD |
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DOI: | https://doi.org/10.1016/j.ica.2013.08.020 |
ISSN: | 0020-1693 |
ISSN: | 1873-3255 |
Titel des übergeordneten Werks (Englisch): | Inorganica chimica acta : the international inorganic chemistry journal |
Verlag: | Elsevier |
Verlagsort: | Lausanne |
Publikationstyp: | Wissenschaftlicher Artikel |
Sprache: | Englisch |
Jahr der Erstveröffentlichung: | 2013 |
Erscheinungsjahr: | 2013 |
Datum der Freischaltung: | 26.03.2017 |
Freies Schlagwort / Tag: | Chelation effect; Extraction; Palladium; Synthesis; Thioether ligands; X-ray diffraction |
Band: | 408 |
Ausgabe: | 2 |
Seitenanzahl: | 6 |
Erste Seite: | 53 |
Letzte Seite: | 58 |
Organisationseinheiten: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
Peer Review: | Referiert |