Journal of Thermal Analysis and Calorimetry

, Volume 134, Issue 3, pp 1829–1837 | Cite as

Thermal behavior study of palladium(II) complexes containing the iminic ligand N,N′-bis(3,4-dimethoxybenzaldehyde) ethane-1,2-diamine

  • T. T. Xavier
  • E. P. de Gois
  • L. E. Sarto
  • E. T. de AlmeidaEmail author


This study describes the synthesis, characterization and thermal behavior study of the Schiff base N,N′-bis(3,4-dimethoxybenzaldehyde)ethane-1,2-diamine (C.1) and four new compounds of palladium(II) N,N-chelate coordination, with the general formula [Pd(X1)(X2)(3,4dm-1,2am)] where 3,4dm-1,2am=N,N′-bis(3,4-dimethoxybenzaldehyde)ethane-1,2-diamine, X1 = X2 = Cl (C.2), X1 = X2 = Cl and Br (C.3), X1 = X2 = N3 (C.4) and X1 = X2 = NCO (C.5). The compounds were characterized by elemental analysis, infrared vibrational spectroscopy (IR) and nuclear magnetic resonance (NMR) 1H and 13C. The TG/DTA curves showed that the thermal decomposition of the C2C.5 complexes occurred in steps that involve the removal of both inorganic and organic ligand, and palladium oxidation steps forming palladium(II) oxide followed by the reduction of PdO into Pd(0), this being the constituent of the residual mass observed at the end of the TG curves, which have values consistent with the expected ones. The formed compounds can be ordered according to thermal stability considering the initial decomposition temperature (C.5>C.2 > C.3>C.4).


Pd(II) complexes Iminic ligand IR and NMR spectroscopy TG–DTA 



We would like to thank CAPES, CNPq, FINEP and FAPEMIG for financial support (Project: CEX - APQ-01984-14). This work is also a collaboration research project of a member of the Rede Mineira de Química (RQ-MG) supported by FAPEMIG (Project: REDE-113/10).

Supplementary material

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Supplementary material 1 (DOCX 887 kb)


  1. 1.
    Farrell NP, Williamson J, Maclaren DJM. Trypanocidal and anti-tumour activity of platinum-metal and platinum-metal-drug dual-function complexes. Biochem Pharmacol. 1984;33:961–71.CrossRefGoogle Scholar
  2. 2.
    Miklášová N, Fischer-Fodor E, Mikláš R, Kucková L, Kožíšek J, Liptaj T, Soritau O, Valentová J, Devínsky F. Synthesis and characterization of new biologically active palladium(II) complexes with (1E,6E)-1,7-bis(3,4-diethoxyphenyl)-1,6-heptadiene-3,5-dione. Inorg Chem Commun. 2014;46:229–33.CrossRefGoogle Scholar
  3. 3.
    Hosny NM, Sherif YE. Synthesis, structural, optical and anti-rheumatic activity of metal complexes derived from (E)-2-amino-N-(1-(2-aminophenyl)ethylidene) benzohydrazide (2-AAB) with Ru(III), Pd(II) and Zr(IV). Spectrochim Acta, Part A. 2015;136:510–9.CrossRefGoogle Scholar
  4. 4.
    Al-Hamdani AAS, Zoubi WA. New metal complexes of N3 tridentate ligand: synthesis, spectral studies and biological activity. Spectrochim Acta, Part A. 2015;137:75–89.CrossRefGoogle Scholar
  5. 5.
    Ali OAM. Characterization, thermal and fluorescence study of Mn(II) and Pd(II) Schiff base complexes. J Therm Anal Calorim. 2017;128:1579–90.CrossRefGoogle Scholar
  6. 6.
    Ahlquist M, Fabrizi G, Cacchi S, Norrby PO. Palladium(0) alkyne complexes as active species: a DFT investigation. Chem Commun. 2005;33:4196–8.CrossRefGoogle Scholar
  7. 7.
    Horino Y, Sugata M, Sugita T, Aimono A, Abe H. Palladium-catalyzed diastereoselective synthesis of homoaldol equivalent products. Tetrahedron Lett. 2017;58:2131–4.CrossRefGoogle Scholar
  8. 8.
    Saldan I, Semenyul Y, Marchuk I. Chemical synthesis and application of palladium nanoparticles. J Mater Sci. 2015;50:2337–54.CrossRefGoogle Scholar
  9. 9.
    Prestianni A, Ferrante F, Sulman EM, Duca D. Density functional theory investigation on the nucleation and growth of small palladium clusters on a hyper-cross-linked polystyrene matrix. J Phys Chem C. 2014;118:21006–13.CrossRefGoogle Scholar
  10. 10.
    Caires ACF, de Almeida ET, Mauro AE, Hemerly JP, Valentini SR. Síntese e atividade citotóxica de alguns azido-ciclopaladados estabilizados com ligantes bifosfínico. Quim Nova. 1999;22(3):329–34.CrossRefGoogle Scholar
  11. 11.
    Cutillas N, Yellol GS, de Haro C, Vicente C, Rodríguez V, Ruiz J. Anticancer cyclometalated complexes of platinum group metals and gold. Coord Chem Rev. 2013;257:2784–97.CrossRefGoogle Scholar
  12. 12.
    Li YG, Zhu HL, Chen XZ, Xin YC, Zhu YH. N,N′-bis(3,4-dimethoxybenzylidene)ethylene-diamine. Acta Crystallogr E. 2006;62:687–8.CrossRefGoogle Scholar
  13. 13.
    Laye RH. Syntheses and photophysical properties of a series of [2:2] silver(I). Inorg Chim Acta. 2007;360:439–47.CrossRefGoogle Scholar
  14. 14.
    Akerdi SJ, Grivani G, Stoeckli-Evans H, Khalaji AD. Crystal structure of dinuclear azide-bridged copper(II) complex [Cu2((3,4-MeO-Ba)2En)21,1–N3)2(N3)2]{(3,4-MeO–Ba)2 En=N,N′-bis(3,4-dimethoxybenzylidene)-1,2-ethanediamine}. Russ J Coord Chem. 2011;37:394–8.CrossRefGoogle Scholar
  15. 15.
    Bego AM, Frem RCG, Netto AVG, Mauro AE, Ananias SR, Carlos IZ, da Rocha MC. Immunomodulatory effects of Palladium(II) complexes of 1,2,4-triazole on murine peritoneal macrophages. J Braz Chem Soc. 2009;20:437–44.CrossRefGoogle Scholar
  16. 16.
    Albert J, Granell J, Luque A, Font-Bardía M, Solans X. Steric and electronic effects on E/Z composition of exocyclic cyclopalladated N-benzylideneamines. J Organmet Chem. 1997;545:131–7.CrossRefGoogle Scholar
  17. 17.
    Bandyopadhyay D, Layek M, Fleck M, Saha R, Rizzoli C. Synthesis, crystal structure and antibacterial activity of azido complexes of cobalt(III) containing heteroaromatic Schiff bases. Inorg Chim Acta. 2017;461:174–82.CrossRefGoogle Scholar
  18. 18.
    Aranha PE, Santos MP, Romera S, Dockal ER. Synthesis, characterization, and spectroscopic studies of tetradentate Schiff base chromium(III) complexes. Polyhedron. 2007;26:1379–82.CrossRefGoogle Scholar
  19. 19.
    Khalajia AD, Grivan G, Rezaei M, Fejfarova K, Dusekc M. Synthesis, spectral characterization, and crystal structure of mononuclear Mercury(II) complex [Hg((3,4-MeO-Bza)2En)I2]. Russ J Coord Chem. 2013;39:104–8.CrossRefGoogle Scholar
  20. 20.
    Walton RA. The infra-red of complexes of palladium(II) and platinum halides with methyl and phenyl cyanides. Spectrochim Acta. 1965;21:1795–801.CrossRefGoogle Scholar
  21. 21.
    da Silva C, da Silva DAM, Rocha FV, Barra CV, Frem RCG, Netto AVG, Mauro AE, de Almeida ET. Synthesis, characterization, and thermal behavior of palladium(II) complexes containing 4-iodopyrazole. J Therm Anal Calorim. 2014;117:1327–34.CrossRefGoogle Scholar
  22. 22.
    Sarto LE, Landre IMR, Bozza GF, Torres C, de Almeida ET. Synthesis and characterization of palladium(II) complexes [PdX2(p-diben)] (X = Cl, Br, I, N3, or NCO; p-diben=N,N′-bis(4-dimethylaminobenzylidene)ethane-1,2-diamine): crystal structure of [Pd(N3)2(p-diben)]. Transit Metal Chem. 2014;39:495–500.CrossRefGoogle Scholar
  23. 23.
    Netto AVG, Takahashi PM, Frem RCG, Mauro AE, Zorel Júnior HE. Thermal decomposition of palladium(II) pyrazolyl complexes. Part I. J Anal Pyrolysis. 2004;72:183–9.CrossRefGoogle Scholar
  24. 24.
    De Almeida ET, Mauro AE, Santana MS, Netto AVG. Emprego de compostos organometálicos mononucleares de paládio(II) na ativação de macrófagos peritoneais de camundongos. Quim Nova. 2005;28:405–8.CrossRefGoogle Scholar
  25. 25.
    Hansen PE, Rozwadowski Z, Dziembowska T. NMR studies of hydroxy Schiff bases. Curr Org Chem. 2009;13:194–215.CrossRefGoogle Scholar
  26. 26.
    Khalaji AD, Weil M, Grivani G, Akerdi SJ. Synthesis, characterization, and crystal structure of two zinc(II) halide complexes with the symmetrical bidentate Schiff-base ligand (3,4-MeO-ba)2en. Monatsh Chem. 2010;141:539–43.CrossRefGoogle Scholar
  27. 27.
    Powder Diffraction File of the Joint Committee on Powder Diffraction Standards. Sets 1-32, published by the International Center of Diffraction Data Swarthmore, PA 19081, USA, 1982.Google Scholar
  28. 28.
    Housecroft CE, Sharpe AG. Inorg Chem. 2nd ed. Harlow: Pearson; 2005.Google Scholar
  29. 29.
    Bozza GF, Sarto LE, Torres C, Netto AVG, Almeida ET. Synthesis and thermal behavior study of complexes of the type [Pd (μ-X)(4-eb-p-phen)]2 (X = Cl, Br, I, N3, NCO, SCN) and 4-eb-p-phen [bis (4-ethylbenzyl) p-phenylenediimine]. J Therm Anal Calorim. 2014;118:67–74.CrossRefGoogle Scholar
  30. 30.
    De Almeida ET, Santana AM, Netto AVG, Torres C, Mauro AE. Thermal study of cyclopalladated complexes of the type [Pd2(-dmba)2X2(bpe)]–(X = NO3, Cl, N3, NCO, NCS; bpe=trans-1,2-bis(4-pyridyl)ethylene). J Therm Anal Calorim. 2005;82:361–4.CrossRefGoogle Scholar
  31. 31.
    Bayer G, Wiedemann HG. Formation, dissociation and expansion behavior of platinum group metal oxides (PdO, RuO2, IrO2). Thermochim Acta. 1975;11:79–88.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  1. 1.Instituto de Química – IQUniversidade Federal de Alfenas - UNIFAL-MGAlfenasBrazil
  2. 2.Instituto Federal de Educação Ciência e Tecnologia do Sul de Minas Gerais – IFSULDEMINASMachadoBrazil

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