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Monatshefte für Chemie - Chemical Monthly

, Volume 146, Issue 1, pp 57–67 | Cite as

New palladium(II) complexes containing 3-mercapto-1,2,4-triazole ligands: synthesis, characterization, crystal structure, and density functional theory calculations

  • Ali Gouranourimi
  • Mitra GhassemzadehEmail author
  • Samira Bahemmat
  • Bernhard Neumüller
  • Ralf Tonner
Original Paper

Abstract

Two new palladium(II) complexes of 4-amino-3-methyl-1,2,4-triazol-5-thione (H3L) have been synthesized and characterized. The reaction of H3L, palladium(II) chloride, and sodium acetate in a molar ratio 2:1:2 gave the homoleptic binuclear palladium(II) complex [Pd2(H2L)4]·2DMSO (1), while its treatment with palladium(II) chloride, sodium acetate, and triphenylphosphane in a molar ratio 4:4:7:4 gave the tetranuclear palladium(II) complex [Pd4(H2L)2(HL)(L)(PPh3)4]Cl·7MeOH·3H2O (2) with terminal phosphane ligands. All complexes have been characterized by a combination of IR, 1H and 31P NMR spectroscopy, ESI(+) mass spectrometry, and elemental analysis as well as X-ray diffraction studies. On the basis of determined molecular structures, each triazole moiety in the binuclear complex is singly deprotonated, whereas the centrosymmetric tetranuclear complex contains three different 3-mercapto-1,2,4-triazolate moieties, namely singly, twofold, and threefold deprotonated in its solid state. In the binuclear complex, the triazolate ligands act as N,S-bidentate bridging ones and coordinate with the metal centers in a trans-(2,2) fashion. In the tetranuclear complex, the four triazolate ligands act as bridging agents between four metal centers through their thiol sulfur atoms and their endocyclic nitrogen atoms in a head-to-head fashion. In addition, each deprotonated NH2 group of the ligand acts as bridging agent between two adjacent palladium metals. According to density functional theory calculations, the structural constraints imposed by the bridging deprotonated NH2 groups are responsible for the observed close Pd–Pd distance in this complex. No indication for metallophilic interactions was found.

Graphical abstract

Keywords

3-Mercapto-1,2,4-triazole Pd(II) complexes Crystal structures DFT calculations 

Notes

Acknowledgments

We thank the Degussa AG for the kind gift of palladium(II) chloride. R.T. thanks the HRZ Marburg for computational resources.

Supplementary material

706_2014_1280_MOESM1_ESM.pdf (82 kb)
Supplementary material 1 (PDF 81 kb)
706_2014_1280_MOESM2_ESM.pdf (208 kb)
Supplementary material 2 (PDF 208 kb)
706_2014_1280_MOESM3_ESM.cif (19 kb)
Supplementary material 3 (CIF 19 kb)
706_2014_1280_MOESM4_ESM.cif (25 kb)
Supplementary material 4 (CIF 25 kb)

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Copyright information

© Springer-Verlag Wien 2014

Authors and Affiliations

  • Ali Gouranourimi
    • 1
  • Mitra Ghassemzadeh
    • 1
    Email author
  • Samira Bahemmat
    • 1
  • Bernhard Neumüller
    • 2
  • Ralf Tonner
    • 2
  1. 1.Department of Inorganic ChemistryChemistry and Chemical Engineering Research Centre of IranTehranIran
  2. 2.Fachbereich ChemiePhilipps UniversitätMarburgGermany

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