3,5-Bis(2-hydroxyphenyl)-1H-1,2,4-triazole based ligands — protonation and metal complex formation
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Stefan Stucky
,
Nadine Koch
Abstract
3,5-Bis(2-hydroxyphenyl)-1H-1,2,4-triazole (H2La) and 4-[3,5-bis(2-hydroxyphenyl)-1H-1,2,4-triazol-1-yl]benzoic acid (H3Lb) have been prepared, and crystal structure of the intermediate 2-(2-hydroxyphenyl)-4H-1,3-benzoxazin-4-one has been determined. Temperature dependent 1H NMR spectroscopic measurements of H2La indicated dynamic behavior with the equilibrium between the two asymmetric tautomers. For H3Lb, pD-dependent 1H NMR spectroscopic measurements showed small but characteristic shifts in the range of 0 ≤ pD ≤ 1, indicative of a triazole nitrogen atom protonation; the corresponding pK a of 0.98 ± 0.04 was determined by spectrophotometric titrations. (H2O, 26°C, 1 M KCl/HCl). Formation of [FeIII(La)]+ (pH 2.5) and [FeIII(La)2]− (pH > 6) was verified by UV-Vis spectroscopy. Complex formation of H3Lb with Al3+ and VO2+ was investigated by 1H NMR spectroscopic titration and cyclic voltammetry, respectively. Single crystals of the phenoxo bridged [VVO(HLb)(EtO)]2·2EtOH were characterized by X-ray structural analysis.
[1] Bentiss, F., Lagrenee, M., Vezin, H., Bouanis, M., & Mernari, B. (2002). An improved procedure for the deamination of symmetrical 3,5-disubstituted 4-amino-1,2,4-triazoles. Journal of Heterocyclic Chemistry, 39, 93–96. http://dx.doi.org/10.1002/jhet.557039011310.1002/jhet.5570390113Suche in Google Scholar
[2] Bernhardt, P. V. (2007). Coordination chemistry and biology of chelators for the treatment of iron overload disorders. Dalton Transactions, 30, 3214–3220. DOI: 10.1039/b708133b. http://dx.doi.org/10.1039/b708133b10.1039/b708133bSuche in Google Scholar
[3] Binstead, R. A., Jung, B., & Zuberbühler, A. D. (2000). SPECFIT/32 (Version 3.0) [computer software]. Marlborough: Spectrum Software Associates. Suche in Google Scholar
[4] Brese, N. E., & O’Keeffe, M. (1991). Bond-valence parameters for solids. Acta Crystallographica Section B, B47, 192–197. DOI: 10.1107/S0108768190011041. 10.1107/S0108768190011041Suche in Google Scholar
[5] Browne, W. R., Ligtenbarg, A. G. J., de Boer, J. W., van den Berg, T. A., Lutz, M., Spek, A. L., Hartl, F., Hage, R., & Feringa, B. L. (2006). Electronic properties, redox behavior, and interactions with H2O2 of pH-sensitive hydroxyphenyl-1,2,4-triazole-based oxovanadium(V) complexes. Inorganic Chemistry, 45, 2903–2916. DOI: 10.1021/ic051848x. http://dx.doi.org/10.1021/ic051848x10.1021/ic051848xSuche in Google Scholar
[6] Crichton, R. R. (2001). Inorganic biochemistry of iron metabolism: From molecular mechanisms to clinical consequences (2nd ed.). Chichester: Wiley. 10.1002/0470845791Suche in Google Scholar
[7] Gampp, H., Maeder, M., Meyer, C. J., & Zuberbühler, A. D. (1985). Calculation of equilibrium constants from multiwavelength spectroscopic data—I. Mathematical considerations. Talanta, 32, 95–101. DOI: 10.1016/0039-9140(85)80035-7. http://dx.doi.org/10.1016/0039-9140(85)80035-710.1016/0039-9140(85)80035-7Suche in Google Scholar
[8] Haasnoot, J. G. (2000). Mononuclear, oligonuclear and polynuclear metal coordination compounds with 1,2,4-triazole derivatives as ligands. Coordination Chemistry Reviews, 200–202, 131–185. DOI: 10.1016/S0010-8545(00)00266-6. http://dx.doi.org/10.1016/S0010-8545(00)00266-610.1016/S0010-8545(00)00266-6Suche in Google Scholar
[9] Hefele, H., Uhlemann, E., & Weller, F. (1997). Vanadium complexes with tridentate diacidic ligands. Bis[2-(2′-hydroxyphenyl)-8-quinolinolato]dimethoxo-dioxo-divanadium(V) — A new structure type. Zeitschrift für Naturforschung B, 52b, 693–695. Suche in Google Scholar
[10] Heinz, U., Hegetschweiler, K., Acklin, P., Faller, B., Lattmann, R., & Schnebli, H. P. (1999). 4-[3,5-Bis(2-hydroxyphenyl)-1,2,4-triazol-1-yl]benzoic acid: A novel efficient and selective iron(III) complexing agent. Angewandte Chemie International Edition, 38, 2568–2570. DOI: 10.1002/(SICI)1521-3773(19990903)38:17〈2568::AID-ANIE2568〉3.0.CO;2-C. http://dx.doi.org/10.1002/(SICI)1521-3773(19990903)38:17<2568::AID-ANIE2568>3.0.CO;2-C10.1002/(SICI)1521-3773(19990903)38:17<2568::AID-ANIE2568>3.0.CO;2-CSuche in Google Scholar
[11] Heinz, U., Sander, J., & Hegetschweiler, K. (2001). Crystal structure of 2-[5-(2-hydroxyphenyl)-1-phenyl-1H-1,2,4-triazol-3-yl]phenol, C20H15N3O2. Zeitschrift für Kristallographie — New Crystal Structures, 216, 113–114. 10.1524/ncrs.2001.216.14.113Suche in Google Scholar
[12] Klingele, M. H., & Brooker, S. (2003). The coordination chemistry of 4-substituted 3,5-di(2-pyridyl)-4H-1,2,4-triazoles and related ligands. Coordination Chemistry Reviews, 241, 119–132. DOI: 10.1016/S0010-8545(03)00049-3. http://dx.doi.org/10.1016/S0010-8545(03)00049-310.1016/S0010-8545(03)00049-3Suche in Google Scholar
[13] Morgenstern, B., Kutzky, B., Neis, C., Stucky, S., Hegetschweiler, K., Garribba, E., & Micera, G. (2007). Synthesis and characterization of vanadium(IV) complexes with cis-inositol in aqueous solution and in the solid-state. Inorganic Chemistry, 46, 3903–3915. DOI: 10.1021/ic0618504. http://dx.doi.org/10.1021/ic061850410.1021/ic0618504Suche in Google Scholar
[14] Morgenstern, B., Steinhauser, S., Hegetschweiler, K., Garribba, E., Micera, G., Sanna, D., & Nagy, L. (2004). Complex formation of vanadium(IV) with 1,3,5-triamino-1,3,5-trideoxy-cisinositol and related ligands. Inorganic Chemistry, 43, 3116–3126. DOI: 10.1021/ic0352046. http://dx.doi.org/10.1021/ic035204610.1021/ic0352046Suche in Google Scholar
[15] Ries, A. (1997). NMR-Tit (A Computer program for the evaluation of NMR-titrations). Saarbrücken: Universität des Saarlandes. Suche in Google Scholar
[16] Ryabukhin, Y. I., Faleeva, L. N., & Korobkova, V. G. (1983). Synthesis of bis(o-hydroxyphenyl)-1,3,5-triazines, 1,2,4-triazoles, and oxadiazole by recyclization of the o-hydroxyphenyl-4-oxo-1,3-benzoxazinium cation. Chemistry of Heterocyclic Compounds, 19, 332–336. DOI: 10.1007/BF00513273. http://dx.doi.org/10.1007/BF0051327310.1007/BF00513273Suche in Google Scholar
[17] Shechter, Y., Goldwaser, I., Mironchik, M., Fridkin, M., & Gefel, D. (2003). Historic perspective and recent developments on the insulin-like actions of vanadium; toward developing vanadium-based drugs for diabetes. Coordination Chemistry Reviews, 237, 3–11. DOI: 10.1016/S0010-8545(02)00302-8. http://dx.doi.org/10.1016/S0010-8545(02)00302-810.1016/S0010-8545(02)00302-8Suche in Google Scholar
[18] Sheldrick, G. M. (1997a). SHELXS-97, Program for crystal structure solution. Göottingen: University of Göttingen. Suche in Google Scholar
[19] Sheldrick, G. M. (1997b). SHELXL-97, Program for crystal structure refinement. Göttingen: University of Göttingen. Suche in Google Scholar
[20] Steinhauser, S., Heinz, U., Bartholomä, M., Weyhermüller, T., Nick, H., & Hegetschweiler, K. (2004a). Complex formation of ICL670 and related ligands with FeIII and FeII. European Journal of Inorganic Chemistry, 21, 4177–4192. DOI: 10.1002/ejic.200400363. http://dx.doi.org/10.1002/ejic.20040036310.1002/ejic.200400363Suche in Google Scholar
[21] Steinhauser, S., Heinz, U., Sander, J., & Hegetschweiler, K. (2004b). Complex formation of 2,6-bis-(2′-hydroxyphenyl) pyridine with AlIII, FeIII and CuII. Zeitschrift für Anorganische und Allgemeine Chemie, 630, 1829–1838. DOI: 10.1002/zaac.200400235. http://dx.doi.org/10.1002/zaac.20040023510.1002/zaac.200400235Suche in Google Scholar
[22] Steinhauser, S., Heinz, U., Bartholomä, M., Weyhermüller, T., Nick, H., & Hegetschweiler, K. (2005). Complex formation of ICL670 and related ligands with FeIII and FeII. European Journal of Inorganic Chemistry, 11, 2262. DOI: 10.1002/ejic.200500302. http://dx.doi.org/10.1002/ejic.20050030210.1002/ejic.200500302Suche in Google Scholar
[23] Stucky, S., Heinz, U., & Hegetschweiler, K. (2007). 3,5-Bis(2-hydroxyphenyl)-1H-1,2,4-triazole and derivatives as effective chelators for hard and highly charged metal cations. In M. Melník, J. Šima, & M. Tatarko (Eds.), XXI. International Conference on Coordination and Bioinorganic Chemistry, Smolenice, 3–8 June, 2007: Achievements in Coordination, Bioinorganic and Applied Inorganic Chemistry (pp. 91–105). Bratislava: Slovak Technical University Press. (http://www.iccbic.stuba.sk/Monograph/091-105.pdf) Suche in Google Scholar
[24] Thompson, K. H., McNeill, J. H., & Orvig, C. (1999). Vanadium compounds as insulin mimics. Chemical Reviews, 99, 2561–2571. DOI: 10.1021/cr980427c. http://dx.doi.org/10.1021/cr980427c10.1021/cr980427cSuche in Google Scholar PubMed
© 2008 Institute of Chemistry, Slovak Academy of Sciences
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Artikel in diesem Heft
- Square-wave adsorptive stripping voltammetric determination of an antihistamine drug astemizole
- Flow injection spectrophotometric determination of iron(III) using diphenylamine-4-sulfonic acid sodium salt
- Sensitive determination of nitrogenous hydrochloride drugs via their reaction with ammonium molybdate
- Effect of different Fe(III) compounds on photosynthetic electron transport in spinach chloroplasts and on iron accumulation in maize plants
- Comparison of different technologies for alginate beads production
- Design and economics of industrial production of fructooligosaccharides
- Preparation of nanocrystalline anatase TiO2 using basic sol-gel method
- 3,5-Bis(2-hydroxyphenyl)-1H-1,2,4-triazole based ligands — protonation and metal complex formation
- Synthesis, characterization, fluorescence and redox features of new vic-dioxime ligand bearing pyrene and its metal complexes
- Synthesis and characterization of diaminomaleonitrile-functionalized polystyrene grafts for application in pervaporation separation
- Synthesis and magnetic properties of polymeric complexes containing ruthenium(II)-ruthenium(III) tetracarboxylato units linked by cyanato, thiocyanato, and selenocyanato ligands
- Preparation and modification of collagen-based porous scaffold for tissue engineering
- Synthesis, crystal structure, and magnetic properties of a cobalt(II) complex with (3,5-dichloropyridin-4-yl)(pyridin-4-yl)methanol
- Synthesis and reactions of 2-[3-(trifluoromethyl)phenyl]furo[3,2-c]pyridine
- Alkalimetric determination of hydrophobic pharmaceuticals using stabilized o/w emulsions
- Extraction and analysis of ellagic acid from novel complex sources
