An Exploratory Study of Tridentate Amine Extractants: Solvent Extraction and Coordination Chemistry of Base Metals with Bis((1R-benzimidazol-2-yl)methyl)amine

DOI: 10.4236/ijnm.2012.13007   PDF   HTML     4,317 Downloads   8,977 Views   Citations


Solvent extraction of base metals using bis((1-decylbenzimidazol-2-yl)methyl)amine (BDNNN) showed a lack of pH-metric separation of the metals. The extraction system was described quantitatively using the equilibria involved to derive the mathematical explanation for the two linear log D vs pHe plots for each metal ion extraction curve, and coordination numbers could also be extracted from the two slopes. The lack of separation was attributed to the absence of stereochemical “tailor making” since the complexes isolated from the reaction of the ligand, bis((1H-benzimidazol- 2-yl)methyl)amine (NNN), with base metals suggested the formation of similar octahedral complex species from spectral and crystal structure evidence. The bis tridentate coordination observed was in agreement with information extracted from the extraction data. This investigation opens up an opportunity and an approach for the evaluation of amines as extractants but cautions against tridentate ligands.

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Magwa, N. , Hosten, E. , Watkins, G. and Tshentu, Z. (2012) An Exploratory Study of Tridentate Amine Extractants: Solvent Extraction and Coordination Chemistry of Base Metals with Bis((1R-benzimidazol-2-yl)methyl)amine. International Journal of Nonferrous Metallurgy, 1, 49-58. doi: 10.4236/ijnm.2012.13007.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] C. Kumar, S. K. Sahu and B. D. Pandey, “Prospects for Solvent Extraction Process in the Indian Context for Recovery of Base Metals. A Review,” Hydrometallurgy, Vol. 103, No. 1-4, 2010, pp. 45-53. HUdoi:10.1016/j.hydromet.2010.02.016U
[2] K. C. Sole, A. M. Feather and P. M. Cole, “Solvent Extraction in Southern Africa: An Update of Some Recent Hydrometallurgical Developments,” Hydrometallurgy, Vol. 78, No. 1-2, 2005, pp. 52-78. HUdoi:10.1016/j.hydromet.2004.11.012U
[3] A. I. Okewole, N. P. Magwa and Z. R. Tshentu, “The Separation of Nickel(II) from Base Metal Ions Using 1-Octyl-2-(2′-pyridyl)imidazole as Extractant in a Highly Acidic Sulfate Medium,” Hydrometallurgy, Vol. 121-124, 2012, pp. 81-89. HUdoi:10.1016/j.hydromet.2012.04.002U
[4] J. G. H. du Preez, J. Postma, S. Ravindran and B. J. A. M. van Brecht, “Nitrogen Reagents in Metal Ion Separation. Part VI. 2-(1′-Octylthiomethyl)pyridine as Extractant for Later 3d Transition Metal Ions,” Solvent Extraction and Ion Exchange, Vol. 15, No. 1, 1997, pp. 79-96. HUdoi:10.1080/07366299708934467U
[5] J. G. H. du Preez, “Recent Advances in Amines as Separating Agents for Metal Ions,” Solvent Extraction and Ion Exchange, Vol. 18, No. 4, 2000, pp. 679-701. HUdoi:10.1080/07366290008934703U
[6] G. D. Christian, “Analytical Chemistry,” 6th Edition, John Wiley and Sons Inc, Hoboken, 2003, pp. 444-445.
[7] R. W. Hay, T. C. Clifford and P. Lightfoot, “Copper(II) and Zinc(II) Complexes of N,N-Bis(benzimidazole-2-ylmethyl)-amine. Synthesis, Formation Constants and the Crystal Structure of [ZnLCl]2]?MeOH. Catalytic Activity of the Complexes in the Hydrolysis of the Phosphotriester 2,4-Dinitrophenyl Diethyl Phosphate,” Polyhedron, Vol. 17, No. 20, 1998, pp. 3575-3581. HUdoi:10.1016/S0277-5387(98)00152-1U
[8] B. Kurzak, D. Kroczewska and J. Jezierska, “Ternary Copper(II) Complexes with Diethylenetriamine and α-(or β-) Alaninehydroxamic Acids in Water Solution,” Polyhedron, Vol. 17, No. 11, 1998, pp. 1831-1841. HUdoi:10.1016/S0277-5387(97)00528-7U
[9] S. O. Bondareva, Y. I. Murinov and V. V. Lisitskii, “Extraction of Non-Ferrous Metals by Bisacylated Diethylenetriamine,” Russian Journal of Inorganic Chemistry, Vol. 52, No. 5, 2007, pp. 796-799. HUdoi:10.1134/S0036023607050257U
[10] J. G. H. du Preez, T. I. A. Gerber, W. Edge, V. L. V. Mtotywa and B. J. A. M. van Brecht, “Nitrogen Reagents in Metal Ion Separation. Part XI. The Synthesis and Extraction Behavior of a New Imidazole Derivative,” Solvent Extraction and Ion Exchange, Vol. 19, No. 1, 2001, pp. 143-154. HUdoi:10.1081/SEI-100001379U
[11] G. Wilkinson, J. A. McCleverty, and R. D. Gillard, Eds.,. Comprehensive Coordination Chemistry, Late Transition Elements, Vol. 5, Pergamon Press, 1987, pp. 596-681.
[12] K. A. Allen, “Equilibrium between Didecylamine and Sulphuric Acid,” Journal of Physical Chemistry, Vol. 60, No. 7, 1956, pp. 943-946. HUdoi:10.1021/j150541a027U
[13] B. R. Reddy, S. V. Rao and K. Ho Park, “Solvent Extraction Separation and Recovery of Cobalt and Nickel from Sulphate Medium using Mixtures of Tops 99 and TIBPS Extractants,” Minerals Engineering, Vol. 22, No. 5, 2009, pp. 500-505. HUdoi:10.1016/j.mineng.2009.01.002U
[14] J. V. Dagdigian and C. A. Reed, “A New Series of Imidazole-Thioether Chelating Ligands for Bioinorganic Copper,” Inorganic Chemistry, Vol. 18, No. 9, 1979, pp. 2623-2626. HUdoi:10.1021/ic50199a058U
[15] M. Haring, “A Novel Route to N-Substituted Heterocycles,” Helvetica Chimica Acta, Vol. 42, 1957, pp. 1845-1850.
[16] Bruker SHELXTL Version 5.1. (includes XS, XL, XP, XSHELL), Bruker AXS Inc., Madison, Wisconsin, USA, 1999.
[17] A. L. Spek, “Single-Crystal Structure Validation with the Program PLATON,” Journal of Applied Crystallography, Vol. 36, 2003, pp. 7-13. HUdoi:10.1107/S0021889802022112U
[18] L. J. Farrugia, “ORTEP-3 for Windows: A Version of ORTEP-III with a Graphical User Interface (GUI),” Journal of Applied Crystallography, Vol. 30, 1997, p. 565. HUdoi:10.1107/S0021889897003117U
[19] H. M. Irving and R. J. P. Williams, “The Stability of Transition Metal Complexes,” Journal of the Chemical Society, 1953, pp. 3192-3210. HUdoi:10.1039/jr9530003192U
[20] D. S. Flett, “Cobalt-Nickel Separation in Hydrometallurgy: A Review,” Chemistry for Sustainable Development, Vol. 12, 2004, pp. 81-91.
[21] L. Alderighi, P. Gans, A. Ienco, D. Peters, A. Sabatini and A. Vacca, “Hyperquad Simulation and Speciation (HySS): A Utility Program for the Investigation of Equilibria Involving Soluble and Partially Soluble Species,” Coordination Chemistry Reviews, Vol. 184, No. 1, 1999, pp. 311-318. HUdoi:10.1016/S0010-8545(98)00260-4U
[22] M. F. Perutz, “The Role of Aromatic Rings as Hydrogen-Bond Acceptors in Molecular Recognition,” Philosophical Transactions: Physical Sciences and Engineering, Vol. 345, No. 1674, 1993, pp. 105-112. HUdoi:10.1098/rsta.1993.0122U
[23] W. J. Geary, “The Use of Conductivity Measurements in Organic Solvents for the Characterisation of Coordination Compounds,” Coordination Chemistry Reviews, Vol. 7, No. 1, 1971, pp. 81-122.
[24] T. J. Lane, I. Nakagawa, J. L. Walker and A. J. Kandathil, “Infrared Investigation of Certain Imidazole Derivatives and Their Metal Chelates,” Inorganic Chemistry, Vol. 1, No. 2, 1962, pp. 267-276. HUdoi:10.1021/ic50002a014U
[25] J. Reedijk, “Pyrazoles and Imidazoles as Ligands. Part VI. Coordination Compounds of Metal(II) Perchlorates, Tetrafluoroborates and Nitrates Containing the Ligand Nn-Butylimidazole,” Journal of Inorganic and Nuclear Chemistry, Vol. 33, No. 1, 1971, pp. 179-188. HUdoi:10.1016/0022-1902(71)80020-9U
[26] E. S. Raper and J. L. Brooks, “Complexes of 1-Methylimidazoline-2-thione with Co(II) and Zn(II) Halides and Perchlorates,” Journal of Inorganic and Nuclear Chemistry, Vol. 39, No. 12, 1977, pp. 2163-2166. HUdoi:10.1016/0022-1902(77)80387-4U
[27] Z. Nakamoto, “Infrared and Raman Spectra of Inorganic and Coordination Compounds,” 3rd Edition, John Wiley and Sons, New York, 1978, p. 239.
[28] A. B. P. Lever, “Inorganic Electronic Spectroscopy,” 2nd Edition, Elsevier, New York, 1984, pp. 554-557.
[29] H. P. Berends and D. W. Stephan, “Copper(I) and Copper(II) Complexes of Biologically Relevant Tridentate Ligands,” Inorganica Chimica Acta, Vol. 93, No. 4, 1984, pp. 173-178. HUdoi:10.1016/S0020-1693(00)88159-1U
[30] J.-Y. Xu, W. Gu, L. Li, S.-P. Yan, P. Cheng, D.-Z. Liao and Z.-H. Jiang, “Synthesis and Crystal Structure of Nickel Complex of N,N-Bis(benzimidazol-2-yl-methyl)amine,” Journal of Molecular Structure, Vol. 644, No. 1-3, 2003, pp. 23-27. HUdoi:10.1016/S0022-2860(02)00281-8U
[31] P. Thangarasu, S. Bernès and C. Durán de Bazúa, “Bis [bis(benzimidazol-2-ylmethyl-N3)amine-N]nickel(II) Dichloride”, Acta Crystallographica Section C-Crystal Structure Communications, Vol. 53, No. 11, 1997, pp. 1607-1609. HUdoi:10.1107/S0108270197006513U

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