TY  - JOUR
A1  - Schwarze, Thomas
A1  - Traeger, Juliane
A1  - Kelling, Alexandra
A1  - Schilde, Uwe
A1  - Holdt, Hans-Jürgen
T1  - Macrocyclic dithiomaleonitriles for an efficient PdCl2 coordination
JF  - Inorganica chimica acta : the international inorganic chemistry journal
N2  - 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 with open-chain dithiomaleonitriles shows the impact of the macrocyclic effect of 4 and 5 on the extraction yield.
KW  - Thioether ligands
KW  - Palladium
KW  - Synthesis
KW  - X-ray diffraction
KW  - Chelation effect
KW  - Extraction
Y1  - 2013
U6  - https://doi.org/10.1016/j.ica.2013.08.020
SN  - 0020-1693
SN  - 1873-3255
VL  - 408
IS  - 2
SP  - 53
EP  - 58
PB  - Elsevier
CY  - Lausanne
ER  -