Thermochemical Parameters of Tetramethylthiourea Adducts of Certain Metal(II) Bromides


Complexes of the general formula [MBr2(TMTU)n] (where M is Mn, Fe, Co, Ni, Cu, Zn or Cd; TMTU is Tetramethylthiourea; n is 0.75, 2 or 3) were obtained by the reaction of salts and ligand in solution. The bromides were selected among several other salts because they had thermochemical data in the literature. Properties as capillary melting points; C, H, N, Br and metal contents; TG/DTG and DSC curves; and IR and electronic spectra were determined. The values of several thermodynamic parameters for the complexes were found by solution calorimetry. From them, the standard enthalpies of the metal-sulphur coordinated bonds were calculated. The standard enthalpies of the formation of the gaseous phase adducts also were estimated.

Share and Cite:

Dunstan, P. (2015) Thermochemical Parameters of Tetramethylthiourea Adducts of Certain Metal(II) Bromides. Open Journal of Physical Chemistry, 5, 9-19. doi: 10.4236/ojpc.2015.51002.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Raja, M.U., Ramesh, R. and Liu, Y. (2011) New Binuclear Pd(II) Thioamide Complexes for the Heck Reaction of Aryl Bromides. Tetrahedron Letters, 52, 5427-5430.
[2] Sah, R., Kumari, S. and Kumar, A. (2011) Synthesis and Characterization of Transition Metal(II) Complexes with HeterocyclicThioamides. Journal of Chemistry, 23, 3563-3565.
[3] Ajaz, H., Hussain, S., Altaf, M., Stoeckli-Evans, H., Isab, A.A., Mahmood, R., Altaf, S. and Ahmad, S. (2011) Synthesis and Characterization of Antimony(III) Complexes of Thioamides, and Crystal Structure of Sb(Imt)2Cl2]2(μ2-Imt)}Cl2 (Imt = Imidazolidine-2-Thione). Chinese Journal of Chemistry, 29, 254-258.
[4] Singh, T. and Singh, K.K. (2010) Synthesis and Characterization of New Ruthenium-Aromatic Thioamidenitrosyls. Oriental Journal of Chemistry, 26, 1171-1174.
[5] Nadeem, S., Rauf, M.K., Bolte, M., Ahmad, S., Tirmizi, S.A., Asna, M. and Hameed, A. (2010) Synthesis, Characterization and Antibacterial Activity of Palladium(II) Bromide Complexes of Thioamides; X-Ray Structure of [Pdf(Tetrametylthiourea)4]Br2. Transition Metal Chemistry, 35, 555-561.
[6] Ozturki, I.I., Hadjikakou, S.K., Hadjiliardis, N., Kourkoumelis, N., Kubicki, M., Tasiopoulos, A.J., Scleiman, H., Barsan, M.M., Butler, I.S. and Balzarini, J. (2009) New Antimony(III) Bromide Complexes with Thioamides: Synthesis, Characterization and Cytotatic Properties. Inorganic Chemistry, 48, 2233-2245.
[7] Sola, J., Lopez, A., Coxall, R.A. and Clegy, W. (2004) Hidrogen-Bonding Network and Layerd Supra-Molecular Structures Assembled from Counterions with Unprecedented Monomeric [AgL2]+ and Chain Polymeric [AgL2]nm+ Complex Cations (L = Thioamide or Thiourea-Like Ligands). Journal of Inorganic Chemistry, 24, 4871-4881.
[8] Sbirna, L.S., Muresan, V., Sbirna, S., Muresan, N. and Lepadatu, C.I. (2004) Complex Compounds of Ions with d6-10 Configuration with Bidentate Heterocyclic Ligands (N, S). Journal of the Indian Chemical Society, 81, 150-152.
[9] Misra, S.K. and Tewari, U.C. (2002) Complexing Behaviour of Aromatic Thioamides (ArCSNHCOR). Transition Metal Complexes of N-Carboethoxy-4-Chlorobenzene and N-Carboethoxy-4-Bromobenzene Thioamide Ligand. Transition Metal Chemistry, 27, 120-125.
[10] Muresan, V., Sbirna, L.S., Sbirna, S., Lepadatu, C.I. and Muresan, N. (2001) Transition Metal Complexes with a New Thioamide of the Dibenzofuran Series. Acta Chimica Slovenica, 48, 439-443.
[11] Neagoe, C., Neagoe, S., Neagoe, O., Cercasov, C. and Lepadatu, C. (1999) Complex Compounds of Pd(II), Pt(II), Cu(I) and Hg(II) with Tertiary Thioamides. Romanian Archives of Microbiology and Immunology, 58, 209-215.
[12] Zalaru, F., Cercasov, C., Meghea, A., Zalaru, C. and Jalen, C. (1991) Copper(II) Coordination Compounds with Thioamides. Revue Roumaine de Chemie, 36, 1279-1285.
[13] Dunstan, P.O. and Dos Santos, L.C.R. (1989) Thermochemistry of Amide and Thioamide Complexes of Arsenic Trihalides. Thermochimica Acta, 156, 163-177.
[14] Desseyn, H.O. (1989) Complexes of Chelates of Amides and Thioamides. Pure and Applied Chemistry, 61, 867-872.
[15] Neagoe, S., Antonescu, L., Negoiu, M., Negoe, V., Negoiuand, D. and Cercasov, C. (1989) Transiton Metal Complexes with Thioamides. Revue Roumaine de Chimie, 34, 845-854.
[16] Carraher Jr., C.E., Chen, W. and Hess, G.G. (1988) Initial Synthesis of Palladium(II) Polyamides and Polythioamides. Polymeric Materials: Science and Engineering, 58, 557-560.
[17] Singh, B. (1987) Studies on Oxovanadium(IV) Complexes of Some Thioamides. Indian Journal of Chemistry Section A, 26, 350-351.
[18] Burns, G.R., DeRoo, C.R., Hall, D.W. and Oliver, A.R. (1987) Chromiun(III) Complexes with Thioamides. Inorganica Chimica Acta, 130, 13-15.
[19] Bret, J.M., Castan, P. and Laurent, J.P. (1983) Studies on Thioamido-Platinum Complexes: Stabilization of Platinum in Its Higher Oxidation State. Transition Metal Chemistry, 8, 218-221.
[20] Muresan, V. and Muresan, N. (1980) Thio Complex Compound Chemistry. Part VIII. Study on the Effect of Ligands and Central Metal Ion on the Nature of Chemical Bond and Structure of Thioamide Complexes. Analete Universitatudin Craiova, 8, 97-101.
[21] Kukushkin, Y.N., Vorob’ev-Desyatovsku, N.V., Sibirskaya, V.V. and Stmkov, V.V. (1980) Some Features of the Behaviour of Platinum(I) Thioamide Complexes in Solutions. Zhurnal Obshchei Khimii, 50, 107-110.
[22] Aarts, A.J., Desseyn, H.O. and Herman, M.A. (1978) Palladium(II) Complexes with Primary Thioamides. Transition Metal Chemistry, 3, 144-146.
[23] Sibirskaya, V.V. and Kukushkin, Y.N. (1978) Thioamide Complexes of Platinum Metals. Koordinatsionnaya Khimiya, 4, 963-991.
[24] Molina, M., Del’acqua, A., Melios, C.V., Azevedo, F.A. and Trabuco, E. (1977) Interaction of the Thioamides with Metals. Complexes in the Solid State and in Solution. Eclética Química, 2, 87-95.
[25] Du Preez, J.G.H. and Gibson, M.L. (1970) Phosphine and Thioamide Complexes of Oxovanadium Dichloride. Journal of the South African Chemical Institute, 23, 184-190.
[26] Niederland, J.B. and Sozzi, J.A. (1958) Microanáslisis Elemental Orgánico. Methopress, Buenos Aires.
[27] Kolthoffand, I.M. and Sandall, E.B. (1956) Tratado de Química Analítica, Cuantitativa. 3rd Edición, Nigar, Buenos Aires.
[28] Flaschka, H.A. (1964) Edta Titrations: An Introduction to Theory and Practice. 2nd Edition, Pergamon Press, London.
[29] Dunstan, P.O. (1999) Thermochemistry of Adducts of Bis(2,4-Pentanedionato)Zinc with Heterocyclic Amines. Journal of Chemical & Engineering Data, 44, 243-247.
[30] Herington, E.F. (1991) Recommended Reference Materials for the Realization of Physicochemical Properties (Recommendation Approved 1974). Pure and Applied Chemistry, 24, 261-289.
[31] Schofer Sr, M. and Curran, C.B. (1966) Infrared Spectra of Complexes of Metal Halides with Tetramethylurea and Tetramethylthiourea. Inorganic Chemistry, 5, 265-268.
[32] Reedijk, J., Van Leeuwem, P.W.N.M. and Groenveld, W.L. (1968) A Semi-Empirical Energy-Level Diagram for Octahedral Nickel Complexes. Recueil des Travaux Chimiques des Pays-Bas, 87, 129-141.
[33] Lever, A.B.P. (1968) Electronic Spectra of Some Transition Metal Complexes. Journal of Chemical Education, 45, 711-712.
[34] Bolster, M.W.G. (1972) The Coordination Chemistry of Amino-Phosphinoxide and Related Compounds. Thesis, Leiden University, Leiden.
[35] Dunstan, P.O. (2009) Thermochemistry of Morpholine Adducts of Some Bivalent Transition Metal Bromides. Journal of Chemical & Engineering Data, 54, 842-846.
[36] Sovast’yanova, T.N. and Suvorov, A.V. (1999) The Structure and Thermal Stability of Group III Halide Complexes with Pyridine. Russian Journal of Coordination Chemistry, 25, 679-688.
[37] Dunstan, P.O. (2004) Thermochemistry of Adducts of Some Transition Metals(II) Bromides with Pyridine N-Oxide. Thermochimica Acta, 409, 19-24.
[38] Wagman, D.D., Evans, W.H., Parker, V.B., Schumm, R.H., Hallow, I.S., Churney, M. and Nuttall, R.L. (1982) The NBS Table of Chemical Thermodynamic Properties. Selected Values for Inorganic and C1 and C2 Organic Substances in SI Units. Journal of Physical and Chemical Reference Data, 2, 50-191.
[39] Kubaschewiski, O., Evans, E.L. and Alcock, C.B. (1967) Metallurgical Thermochemistry. 4th Edition, Pergamon Press, London.
[40] Inagari, S.C., Murata, S. and Sakiyama, M. (1982) Thermochemical Studies on Thioacetamide and Tetramethylthiourea. Estimation of Stabilization Energies Due to Interaction between Thiocarbonyl Group and Neighboring Nitrogen Atom. Bulletin of the Chemical Society of Japan, 55, 2808-2813.
[41] Skinner, H.A. and Pilcher, G. (1963) Bond Energy-Term Values in Hydrocarbons and Related Compounds. Quarterly Reviews, Chemical Society, 17, 264-288.

Copyright © 2022 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.