Abstract
Proton NMR was used to study the complexation reaction of Ag+ with octathia-24-crown-8 (OT24C8) in a number of binary dimethylsulfoxide (DMSO)–nitrobenzene (NB) mixtures at different temperatures. In all cases, the exchange between free and complexed OT24C8 was fast on the NMR time scale and only a single population average 1H signal was observed. The formation constants of the resulting 1:1 complexes in different solvent mixtures were determined by computer fitting of the chemical shift-mole ratio data. There is an inverse relationship between the complex stability and the amount of DMSO in the solvent mixtures. The enthalpy and entropy values for the complexation reaction were evaluated from the temperature dependence of formation constants. In all solvent mixtures studied, the resulting complex is enthalpy stabilized but entropy destabilized. The TΔS° versus ΔH° plot of all thermodynamic data obtained shows a fairly good linear correlation indicating the existence of enthalpy–entropy compensation in the complexation reaction.
Similar content being viewed by others
References
Izatt, R.M., Bradshaw, J.S., Nielsen, S.A., Lamb, J.D., Christensen, J.J; Sen, D.: Thermodynamic and kinetic data for cation-macrocycle interaction. Chem. Rev. 85, 271–339 (1985)
Izatt, R.M., Pawlak, K., Bradshaw, J.S., Bruening, R.L.: Thermodynamic and kinetic data for macrocycle interaction with cations and anions. Chem. Rev. 91, 1721–2085 (1991)
Izatt, R.M., Pawlak, K., Bradshaw, J.S., Bruening, R.L.: Thermodynamic and kinetic data for macrocycle interaction with cations, anions, and neutral molecules. Chem. Rev. 95, 2529–2586 (1995)
Cooper, S.R., Rawle, S.C.: Crown thioether chemistry. Struct. Bonding (Berlin) 72, 1–72 (1990)
Glenny, M.W., van de Water, L.G.A., Vere, J.M., Blake, A.J., Wilson, C., Driessen, W.L., Reedijk, J., Schroder, M.: Improved synthetic methods to mixed-donor thiacrown ethers. Polyhedron 25, 599–612 (2006)
Forsyth, G.A., Lockhart, J.C.: Criteria to judge preorganization study of known and the design of new thiocrown ethers. J. Chem. Soc. Dalton Trans. 2243–2249 (1994)
Danks, J.P., Champness, N.R., Schroder, M.: Chemistry of mixed nitrogen- and sulfur-donor and tridentate macrocycles. Coord. Chem. Rev. 174, 417–468 (1998)
Madeu-Bulto, A.M., Dieguez, M., Artin, E.M., Gomez, M.: Chiral thioether ligands: coordination chemistry and asymmetric catalysis. Coord. Chem. Rev. 242, 159 (2003)
Blake, A.J., Halcrow, M.A., Schroder, M.: Organometallic macrocyclic chemistry - Synthesis of cationic half-sandwich iridium(I) complexes of 1,4,7-trithiacyclononane ([9]aneS3) - Crystal-structures of [Ir([9]aneS3)(C2H4)]PF6, [Ir([9]aneS3)(C8H12)]PF6 and [Ir([9]aneS3)(C4H6)PF6.0.5et2O. J. Chem Soc. Dalton Trans. 1631–1639 (1994)
Kim, H.-J., Lee, J.H., Suh, I.H., Do, Y.: A novel route to dinuclear heteroleptic rhodium(III) complexes of 1,4,7-trithiacyclononane. Inorg. Chem. 34, 796–801 (1995)
Grant, G.J., Rogers, K.E., Setzer, W.N., Van Derveer, D.J.: Crown thioether complexes of trivalent transition-metal ions - The crystal-structure of [cr(18S6)Cl-3]. Inorg. Chim. Acta 234, 35–45 (1995)
Landgrafe, C., Sheldrick, W.S.: Dinuclear thioether half-sandwich ruthenium(II) complexes of the types [{RuL’([9]aneS(3))}(2)(mu-L)(n)](2+) (n=1, L’ = PPh(3); n=2, L’=MeCN), [{Ru([9]aneS(3))}(2)(mu-L)(2)](2+) and [{Ru([9]aneS(3))}(2) (mu-L)(3)](+) with heterocyclic thioamides L ([9]aneS(3)=1,4,7-trithiacyclononane). J. Chem. Soc. Dalton Trans. 989–998 (1996)
Adams, R.D., Fallen, S.B., Perrrin, J.L., Queisser, J.A., Yamamoto, J.H.: The catalytic ring-opening of cyclooligomerization (ROC) of thietane by the complexes M(CO)(5)L (M=Cr and W; L=CO, thietane and 1,5,9-trithiacyclododecane). Chem. Ber. 129, 313–318 (1996)
Blake, A.J., Li W.-S., Lippolis, V., Taylor, A., Schroder, M.: Mercury(II), silver(I) and gold(I) thioether crown chemistry: Synthesis, electrochemistry and structures of [(HgBr2)(2)([24]aneS(8))], [{Ag2([24]aneS(8))(CF3SO3)(2) (MeCN)(2)}(infinity)],[Ag2([28]aneS(8))][NO3](2) and [Au2([28]aneS(8))] [PF6](2) ([24]aneS(8) = 1,4,7,10,13,16,19,22-octathia-cyclotetracosane; [28]aneS(8) = 1,4,8,11,15,18,22,25-octathiacyclo-octacosane). J. Chem. Soc. Dalton Trans. 2931–2937 (1998)
Blake, A.J., Lippolis, V., Parsons, S., Schroder, M.: Catena-poly[[trans-dichloro-copper(II)]-mu-1,4,7,10,13,16-hexathia-cyclooctadecane-S-1:S-10]. Acta Crystallogr. C 57, 36–37 (2001)
Naito, T., Nishibe K., Inabe T.: New binuclear copper complexes [(9S3)Cu(CN)Cu(9S3)]Xn (X=BF4, n=1; X=TCNQ, n=2) (9S3=1,4,7-trithiacyclononane): Syntheses, crystal structures and magentic properties: Z. Anorg. Allg. Chem. 630, 2725–2730 (2004)
Lippolis, V., Shamsipur, M.: Synthesis, coordination properties and analytical applications of mixed donor macrocycles containing the 1,10-phenanthroline sub-unit. J. Iran. Chem. Soc. 3, 105–127 (2006)
Saito, K., Murakami, S., Muromatsu A., Sekido E.: Extraction behavior of silver(I) with some cyclic tetrathioethers. Polyhedron 12, 1587–1591 (1993)
Moyer, B.A., Delmau, L.H., Case, G.N., Bajo, S., Baes, C.F.: Comprehensive equilibrium-analysis of the complexation of Cu(II) by tetrathia-14-crown-4 in a synergistic extraction system employing didodecylnaphthalene sulfonic-acid. Sep. Sci. Technol. 30, 1047–1069 (1995)
Yamini, Y., Alizadeh, N., Shamsipur, M.: Solid phase extraction and determination of ultra trace amounts of mercury(II) using octadecyl silica membrane disks modified by hexathia-18-crown-6-tetraone and cold vapor atomic absorption spectrometry. Anal. Chim. Acta. 355, 69–74 (1997)
Shamsipur, M., Mashhadizadeh, M.H.: Preconcentration of trace amounts of silver ion in aqueous samples on octadecyl silica membrane disks modified with hexathia-18-crown-6 and its determination by atomic absorption spectrometry. Fresenius J. Anal. Chem. 367, 246–249 (2000)
Shamsipur, M., Mashhadizadeh, M.H.: Highly efficient and selective membrane transport of silver(I) using hexathia-18-crown-6 as a specific ion carrier. Sep. Purif. Technol. 20, 147–153 (2000)
Shamsipur, M., Azimi, G., Mashhadizadeh, M.H., Madaeni, S.S.: Selective transport of silver ion through a supported liquid membrane using hexathia-18-crown-6 as carrier: Anal. Sci. 17, 491–495 (2001)
Mashhadizadeh, M.H., Mohyaddini, R., Shamsipur, M.: Selective and efficient liquid membrane transport of Au(III) by tetrathia-12-crown-4 as a specific carrier. Sep. Purif. Technol. 39, 161–166 (2004)
Shamsipur, M., Hashemi, O.R., Lippolis, V.: A supported liquid membrane system for simultaneous separation of silver(I) and mercury(II) from dilute feed solutions. J. Membr. Sci. 282, 322–327 (2006)
Fakhari, A.R., Ganjali, M.R., Shamsipur, M.: PVC-based hexathia-18-crown-6-tetraone sensor for mercury(II) ions. Anal. Chem. 69, 3693–3696 (1997)
Mashhadizadeh, M.H., Shamsipur, M.: Silver(I)-selective membrane electrode based on hexathia-18-crown-6. Anal. Chim. Acta. 381, 111–116 (1999)
Shamsipur, M., Mashhadizadeh, M.H.: Cadmium ion selective electrode based on tetrathia-12-crown-4. Talanta. 53, 1065–1071 (2001)
Mashhadizadeh, M.H., Mostafavi, A., Razavi, R., Shamsipur, M.: Highly selective and sensitive Cu(II) PVC membrane electrode based on 3,6,9,14-tetrathiabicyclo[9.2.1.]tetradeca-11,13-diene as a suitable neutral ionophore. Sens. Actuators B 86, 222–228 (2002)
Murray, S.G., Hartley, F.R.: Coordination chemistry of thioethers, selenoethers, and telluroethers in transition-metal complexes. Chem. Rev. 81, 365–414 (1981)
Alizadeh, N., Shamsipur, M.: Nuclear magnetic resonance study of the ligand interchange of 18-crown-6 complexes with La3+, Ca2+, Pb2+ and Ba2+ ions in 70% methanol solution. J. Chem. Soc. Faraday Trans. 92, 4391–4394 (1996)
Alizadeh, N., Shamsipur, M.: Nuclear magnetic resonance study of the ligand interchange of Ba2+-18-crown-6 complex in methanol solution. J. Solution Chem. 25, 1029–1039 (1996)
Fakhari, A.R., Shamsipur, M.: An NMR study of the stoichiometry and stability of lithium ion complexes with 12-crown-4, 15-crown-5 and 18-crown-6 in binary acetonitrile-nitrobenzene mixtures. J. Incl. Phenom. 26, 243–251 (1996)
Shamsipur, M., Alizadeh, N.: NMR study of the ligand interchange of hexacyclen and hexamethylhexacyclen complexes with Tl+ ion in 70% methanol solution. J. Chin. Chem. Soc. 45, 241–247 (1998)
Fakhari, A.R., Shamsipur, M.: Proton NMR study of the ligand interchange of the Ba2+-18-crown-6 complex in binary acetonitrile-water mixtures. J. Incl. Phenom. 32, 405–414 (1998)
Shamsipur, M., Talebpour, Z., Alizadeh, N.: NMR study of the stoichiometry, stability and ligand interchange of silver ion-hexathia-18-crown-6 complex in binary dimethylsulfoxide-acetonitrile and dimethylsulfoxide-methanol solvent mixtures at 300 K. J. Solution Chem. 32, 227–238 (2003)
Talebpour, Z., Alizadeh, N., Bijanzadeh, H.R., Shamsipur, M.: Cadmium-113 NMR and theoretical studies of complexation of 15-crowns-5 and benzo-15-crown-5 in acetonitrile and its binary mixtures with water and nitromethane. J. Incl. Phenom. 49, 101–106 (2004)
Alizadeh, N., Bordbar, M., Shamsipur, M.: Proton NMR investigation of the stoichiometry, stability and exchange kinetics of Tl+ complexes with hexacyclen and hexamethylhexacyclen in dimethylformamide solutions. Observation of a three site exchange process. Bull. Chem Soc. Jpn. 78, 1763–1772 (2005)
Bordbar, M., Shamsipur, M., Alizadeh, N.: 1H NMR studies of homo and mixed ligand complexes of Tl+ ion with several polyazamacrocycles. Bioorg. Med. Chem. 13, 2253–2262 (2005)
Nicely, V.A., Dye, J.L.: A general purpose curve fitting program for class and research use. J. Chem. Educ. 48, 443–447 (1971)
Cahen, Y.M., Dye, J.L., Popov, A.I.: Lithium-7 nuclear magnetic resonance study of lithium cryptates in various solvents. J. Phys. Chem. 79, 1289–1291 (1975)
Blake, A.J., Li W.-S., Lippolis, V., Schroder, M.: Thioether macrocycles as spacers for crystal engineering: synthesis and crystal structures of [Ag2([24]aneS(8))(CF3SO3)(2)(MeCN)(2)](infinity) and [Ag([16]aneS(4))(BF4)] (infinity)([24]aneS(8) = 1,4,7,10,13,16,19,22-octathiacyclotetracosane; [16]aneS(4) = ,1,5,9,13-tetrathiacyclohexadecane). Chem. Commun. 1943–1944 (1977)
Hyperchem, Release 502, Hypercube, Inc., Gainesville, 1997
Gutmann, V.: Coordination Chemistry in Nonaqueous Solvents, Springer-Verlag, Vienna, 1968
Izatt, R.M., Terry, R.E., Nelson, D.P., Chan, Y., Eatough, D.J., Bradshaw, J.S., Hansen, L.D., Christensen, J.J.: Calorimetric titration study of the interaction of some uni- and bivalent cations with benzo-15-crown-5, 18-crown-6, dibenzo-24-crown-8, and dibenzo-27-crown-9 in methanol-water solvents, at 25.degree C and mu = 0.1. J. Am. Chem. Soc. 98, 7626–7630 (1976)
Cox, B.G., Firman, P., Gudin, D., Schneider, H.: Potentiometric and proton NMR studies on the solvation of cryptand (222) and its complexes with potassium(1+) and silver(1+) in acetonitrile water mixtures. J. Phys. Chem. 86, 4988–4992 (1982)
Rouhollahi, A., Amini, M.K., Shamsipur, M.: NMR study of the stoichiometry, stability and exchange kinetics of complexation reaction between Pb2+ ion and 18-crown-6 in binary acetonitrile-water mixtures. J. Solution Chem. 23, 63–74 (1994)
Ghasemi, J., Shamsipur, M.: Conductance study of some transition and heavy metal complexes with 1,10-diaza-18-crown-6 in binary acetonitrile-dimethylsulfoxide mixtures. J. Solution Chem. 25, 485–504 (1996)
Shamsipur, M., Pouretedal, H.R.: Conductance study of complexation of lead ions with several 18-membered crown ethers in binary acetonitrile-dimethylsulfoxide mixtures between 25 and 55 °C. J. Solution Chem. 28, 1187–1205 (1999)
Shamsipur, M., Popov, A.I.: Multinuclear NMR study of dibenzo-30-crown-10 complexes with sodium, potassium, and cesium ions in nonaqueous solvents. J. Am. Chem. Soc. 101, 4051–4055 (1979)
Inoue, Y., Takushi, T., Liu, Y., Tong, L.-H., Lin, D.S.: Thermodynamics of molecular recognition by cyclodextrins. 1. Calorimetric titration of inclusion complexation of naphthalenesulfonates with alpha-cyclodextrin, beta-cyclodextrin, and gamma-cyclodextrin - Enthalpy entropy compensation. J. Am. Chem. Soc. 115, 475–481 (1993)
Visser, H.C., Reinhoudt, D.N., de Jong, F.: Carrier-mediated transport through liquid membranes. Chem. Soc. Rev. 75–82 (1994)
Grunwald, E., Steel, C.: Solvent reorganization and thermodynamic enthalpy-entropy compensation. J. Am. Chem. Soc. 117, 5687–5692 (1995)
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Shamsipur, M., Irandoust, M., Alizadeh, K. et al. Proton NMR study of the stoichiometry, stability and thermodynamics of complexation of Ag+ ion with octathia-24-crown-8 in binary dimethylsulfoxide–nitrobenzene mixtures. J Incl Phenom Macrocycl Chem 59, 203–209 (2007). https://doi.org/10.1007/s10847-007-9317-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10847-007-9317-0