View More View Less
  • 1 Departamento de Química Geral e Inorgânica, Instituto de Química de Araraquara, UNESP—Univ Estadual Paulista, P.O. Box 355, Araraquara, SP, 14801-970, Brazil
  • | 2 Departamento de Ciências Exatas, Universidade Federal de Alfenas, UNIFAL, Alfenas, MG, 37130-000, Brazil
Restricted access

Abstract

This work describes the synthesis, characterization, and the thermal behavior investigation of four palladium(II) complexes with general formulae [PdX2(mba)2], in which mba = N-methylbenzylamine and X = OAc (1), Cl (2), Br (3) or I (4). The complexes were characterized by elemental analysis, infrared vibrational spectroscopy, and 1H nuclear magnetic resonance. The stoichiometry of the complexes was established by means of elemental analysis and thermogravimetry (TG). TG/DTA curves showed that the thermodecomposition of the four complexes occurred in 3–4 steps, leading to metallic palladium as final residue. The palladium content found in all curves was in agreement with the mass percentages calculated for the complexes. The following thermal stability sequence was found: 3 > 2 > 4 > 1. The geometry optimization of 1, 2, 3, and 4, calculated using the DFT/B3LYP method, yielded a slightly distorted square planar environment around the Pd(II) ion made by two anionic groups and two nitrogen atoms from the mba ligand (N1 and N2), in a trans-relationship.

  • 1. La Deda, M, Ghedini, M, Aiello, I, Pugliese, T, Barigelletti, F, Accorsi, G. Organometallic emitting dyes: palladium(II) nile red complexes. J Organomet Chem. 2005;690:857861. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 2. Yasuike, S, Okajima, S, Yamaguchi, K, Seki, H, Kurita, J. New optically active organoantimony (BINASb) and bismuth (BINABi) compounds comprising a 1,1′-binaphtyl core: synthesis and their use in transition metal-catalysed asymmetric hydolysation of ketones. Tetrahedron. 2003;59:49594966. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 3. Kurzeev, SA, Kazankov, GM, Ryabov, AD. Increased catalytic activity of primary amine palladacycles in biomimetic hydrolysis of N-t-BOC-S-methionine p-nitrophenyl ester. Inorg Chim Acta. 2000;305:16. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 4. Díez, L, Espinet, P, Miguel, JA, Rodríguez-Medina, MP. Mesogens based on plalladium orthometallated complexes with carboxylato bridges: tuning and shaping a non-planar molecule. J Organomet Chem. 2005;690:261268. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 5. Caires, ACF, de Almeida, ET, Mauro, AE, Hemerly, JP, Valentini, SR. Síntese e atividade citotóxica de alguns azido-ciclopaladados estabilizados com ligantes bifosfínicos. Quim Nova. 1999;22:329334. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 6. Tomita, K, Caires, ACF, Neto, VAD, Mauro, AE. Structure of a cyclopalladated complex, [PdCl(C37H32N)]. Acta Cryst C. 1994;50:18721873. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 7. Stevanato, A, Mauro, AE, Netto, AVG. Thermal spectroscopic investigation on NN-dimethylbenzylamine based cyclopalladated compounds containing isonicotinamide. J Therm Anal Calorim. 2009;97:149152. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 8. de Almeida, ET, Santana, AM, Netto, AVG, Torres, C, Mauro, AE. Thermal study of cyclopalladated complexes of the type [Pd2(dmba)2X2(bpe)]. J Therm Anal Calorim. 2005;82:361364. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 9. Moro, AC, Mauro, AE, Netto, AVG, Ananias, SR, Quilles, MB, Carlos, IZ, Pavan, FR, Leite, CQF, Hörner, M. Antitumor and antimycobacterial activities of cyclopalladated complexes: X-ray structure of [Pd(C2, N-dmba)(Br)(tu)] (dmba=N, N-dimethylbenzylamine, tu=thiourea). Eur J Med Chem. 2009;44:46114615. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 10. Rocha, MC, Santana, AM, Ananias, SR, de Almeida, ET, Mauro, AE, Placeres, MCP, Carlos, IZ. Citotoxicity and immune response induced by organopalladium(II) in mice bearing Ehrlich ascites tumor. J Braz Chem Soc. 2007;18:14731480. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 11. de Almeida, ET, Mauro, AE, Santana, AM, Netto, AVG. Emprego de compostos organometálicos mononucleares de paládio(II) na ativação de macrófagos peritoneais de camundongos. Quim Nova. 2005;28:405408. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 12. de Almeida, ET, Mauro, AE, Santana, AM, Ananias, SR, Netto, AVG, Ferreira, JG, Santos, RHA. Self-assembly of organometallic Pd(II) complexes via CH3 π interactions: the first example of a cyclopalladated compound with herringbone stacking pattern. Inorg Chem Commun. 2007;10:13941398. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 13. Mauro, AE, Caires, ACF, Santos, RHD, Gambardella, MTD. Cycloaddition reaction of the azido-bridged cyclometallated complex [Pd(dmba)N3]2 with CS2. Crystal and molecular structure of di(μ-N, S-1,2,3,4,-thiatriazole-5-thiolate)bis[N,N-dimethylbenzyl-amine-C2, N)palladium(II)]. J Coord Chem. 1999;48:521528. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 14. Santana, AM, Mauro, AE, Almeida, ET, Netto, AVG, Klein, SI, Santos, RHA, Zoia, JR. 1,3-Diploar cycloaddition of CS2 to the coordination azide in the cyclopalladated [Pd(bzan)(μ-N3)]2. Crystal and molecular structure of di(μ-N, S-1,2,3,4-thiatrizole-5-thiolate)bis[(benzylideneaniline-C2, N)palladium(II)]. J Coord Chem. 2001;53:163172. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 15. Ananias, SR, Santana, AM, Mauro, AE, Neto, VAL, de Almeida, ET. Reação de bis-inserção de 1,2-difenilacetileno na ligação Pd–C de ciclometalados. Quim Nova. 2003;26:5355. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 16. Fuchita, Y, Tsuchiya, H, Miyafuji, A. Cyclopalladation of secondary and primary benzylamines. Inorg Chim Acta. 1995;233:9196. .

  • 17. Legendre, AO, Mauro, AE, Ferreira, JG, Ananias, SR, Santos, RHA, Netto, AVG. A 2D coordination polymer with brick-wall network topology based on the [Cu(NCS)2(pn)] monomer. Inorg Chem Commun. 2007;10:815820. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 18. Netto, AVG, Frem, RCG, Mauro, AE. Low-weight coordination polymers derived from the self-assembly reactions of Pd(II) pyrazolyl compounds and azide ion. Polyhedron. 2005;24:10861092. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 19. Netto, AVG, Frem, RCG, Mauro, AE. Synthesis and spectroscopic characterization of a novel coordination polymer of palladium(II) with pyrazole and azido ligands. Mol Cryst Liq Cryst. 2002;374:255260.

    • Search Google Scholar
    • Export Citation
  • 20. Netto, AVG, Mauro, AE, Frem, RCG, Santana, AM, Santos, RHA, Zoia, JR. Synthesis and structural characterization of dichlorobis(1-phenyl-3-methylpyrazole)palladium(II) and diazidobis(1-phenyl-3-methylpyrazole)palladium(II). J Coord Chem. 2001;54:129141. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 21. Rocha, FV, Barra, CV, Netto, AVG, Mauro, AE, Carlos, IZ, Frem, RCG, Ananias, SR, Quilles, MB, Stevanato, A, Rocha, MC. 3,5-Dimethyl-1-thiocarbamoylpyrazole and its Pd(II) complexes: synthesis, spectral studies and antitumor activity. Eur J Med Chem. 2010;45:16981702. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 22. de Souza, RA, Stevanato, A, Treu-Filho, O, Netto, AVG, Mauro, AE, Castellano, EE, Carlos, IZ, Pavan, FR, Leite, CQF. Antimycobacterial and antitumor activities of palladium(II) complexes containing isonicotinamide (isn): X-ray structure of trans-[Pd(N3)2(isn)2]. Eur J Med Chem. 2010;45:48634868. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 23. Netto, AVG, Takahashi, PM, Frem, RCG, Mauro, AE, Zorel Júnior, HE. Thermal decomposition of palladium(II) pyrazolyl complexes. Part I. J Anal Appl Pyrolysis. 2004;72:183189. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 24. Netto, AVG, Santana, AM, Mauro, AE, Frem, RCG, de Almeida, ET, Crespi, MS, Zorel Júnior, HE. Thermal decomposition of palladium(II) pyrazolyl complexes. Part II. J Therm Anal Calorim. 2005;79:339342. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 25. Netto, AVG, Frem, RCG, Mauro, AE, Crespi, MS, Zorel Júnior, HE. Synthesis, spectral and thermal studies on pyrazolate-bridged palladium(II) coordination polymers. J Therm Anal Calorim. 2007;87:789792. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 26. Fernandes, RL, Takahashi, PM, Frem, RCG, Netto, AVG, Mauro, AE, Matos, JR. Synthesis, spectral and thermal studies on dicarboxylate-bridged palladium(II) coordination polymers. Part I. J Therm Anal Calorim. 2009;97:123126. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 27. Fernandes, RL, Takahashi, PM, Frem, RCG, Netto, AVG, Mauro, AE, Matos, JR. Synthesis, spectral and thermal studies on dicarboxylate-bridged palladium(II) coordination polymers. Part II. J Therm Anal Calorim. 2009;97:153156. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 28. 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).

    • Search Google Scholar
    • Export Citation
  • 29. Becke, AD. Density-functional thermochemistry III. The role of exact exchange. J Chem Phys. 1993;98:56485652. .

  • 30. Lee, C, Yang, W, Parr, RG. Development of the Colle–Salvetti correlation energy formula into a functional of the energy density. Phys Rev B. 1988;37:785789. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 31. Treu-Filho, O, Pinheiro, JC, da Costa, EB, Ferreira, JEV, de Figueiredo, AF, Kondo, RT, de Lucca Neto, VA, de Souza, RA, Legendre, AO, Mauro, AE. Experimental and theoretical study of the compound [Pd(dmba)(NCO)(imz)]. J Mol Struct. 2007;829:195201. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 32. Treu-Filho, O, Pinheiro, JC, de Souza, RA, Kondo, RT, Ferreira, RDP, de Figueiredo, AF, Mauro, AE. Molecular structures and vibrational frequencies for cis-[PdCl2(tmen)] and cis-[Pd(N3)2(tmen)]: a DFT study. Inorg Chem Commun. 2007;100:15011504. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 33. Li, X, Frisch, MJ. Energy-represented DIIS within a hybrid geometry optimization method. J Chem Theory Comput. 2006;2:835839. .

  • 34. Frisch MJ , Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery Jr. JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth AG, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ, Gaussian 09, Revision A.02. Wallingford, CT: Gaussian, Inc.; 2009.

    • Search Google Scholar
    • Export Citation
  • 35. GaussView 5.0.8: Copyright (c) 2000–2008 Semichem, Inc.

  • 36. Nakamoto, K. Infrared and Raman spectra for inorganic and coordination compounds. Part B: applications in coordination, organometallic, and bioinorganic chemistry. 5 New York: Wiley-Interscience Publication; 1997.

    • Search Google Scholar
    • Export Citation
  • 37. Sui-Seng C , Zargarian D. trans-Bis(benzylamine)dichloropalladium(II). Acta Cryst E. 2003;E59:m9578.

  • 38. Clifford, SE, Tiwow, V, Gendron, A, Maeder, M, Rossignoli, M, Lawrance, GA, Turner, P, Blake, AJ, Schröder, M. Complexation of constrained ligands piperazine, N-substituted piperazines, and thiomorpholine. Aust J Chem. 2009;62:11961206. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 39. Ha, K. Crystal structure of diiodobis(acridine)palladium(II), PdI2(C13H9N)2. Z. Kristallogr. NCS. 2010;225:693694.

  • 40. Halligudi, SB, Bhatt, KN, Khan, NH, Kurashy, RI, Venkatsubramanian, K. Synthesis, structural characterization and catalytic carbonylation of nitrobenzene and amines by mononuclear palladium(II) complexes containing substituted pyridine ligands. Polyhedron. 1996;15:20932101. .

    • Crossref
    • Search Google Scholar
    • Export Citation