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Issue 7, 2014
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Further orthometalated dinuclear palladium(III) compounds with bridging N,S-donor ligands

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New dinuclear palladium(III) compounds of general formula Pd2[(C6H4)PPh2]2[N–S]2Cl2, N–S being 2-mercaptopyridinate, 3a; 2-mercapto-6-methylpyridinate, 3b; 2-quinolinethiolate, 3c; 2-mercaptopyrimidinate, 3d; 1-methyl-1H-imidazole-2-thiolate, 3e; 1-methyl-1H-benzimidazole-2-thiolate, 3f; 2-mercaptobenzothiazolate, 3g and 5-mercapto-1-methyltetrazolate, 3h have been obtained by oxidation with PhICl2 of the corresponding palladium(II) counterparts. The stability of the new compounds has been studied by 31P NMR spectroscopy from 200 to 298 K. Compounds 3f–h were relatively stable until room temperature and they have been synthesized and characterized by 31P, 1H and 13C NMR spectroscopy at 223 K. Compound 3h was also structurally characterized by single X-ray diffraction methods at 150 K showing a Pd–Pd distance of 2.6334(6) Å. A topological charge density analysis has also been performed in order to obtain information on the nature of the bonding in these new palladium(II) and (III) compounds. The contribution of the sulphur p orbitals to the HOMO orbitals in the oxidized compounds allows greater stabilization.

Graphical abstract: Further orthometalated dinuclear palladium(iii) compounds with bridging N,S-donor ligands

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The article was received on 30 Sep 2013, accepted on 29 Nov 2013 and first published on 02 Dec 2013

Article type: Paper
DOI: 10.1039/C3DT52717D
Citation: Dalton Trans., 2014,43, 2961-2970
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    Further orthometalated dinuclear palladium(III) compounds with bridging N,S-donor ligands

    S. Ibáñez, D. N. Vrečko, F. Estevan, P. Hirva, M. Sanaú and M. xmlns="http://www.rsc.org/schema/rscart38"> <. Úbeda, Dalton Trans., 2014, 43, 2961
    DOI: 10.1039/C3DT52717D

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