Abstract
The host–guest molecular complexationreaction between cryptand C222 and iodine has beenstudied spectrophotometrically in 1,2-dichloroethanesolution. The resulting 1 : 1 and 2 : 1 (I2 to C222)complexes were formulated as (C222 β I+)I-and (C222 β I+)I3 -, respectively. Theenthalpy and entropy of the complex formationreactions were evaluated from the temperaturedependence of the formation constants. The resultingcomplexes are both enthalpy and entropy stabilized.The spectrophotometric, NMR, conductometric andpotentiometric results emphasize that the complexesare positive iodine cryptates. The rate constants forthe formation and proton-assisted dissociation of the(C222 β I+)I3 - complex at varioustemperatures and the corresponding activationparameters were evaluated. Based on the results thusobtained, possible pathways for the complexationreaction are proposed.
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References
L. J. Andrews and R. M. Keefer: Molecular Complexes in Organic Chemistry, Holden-Day, New York (1962).
R. Foster: Organic Charge-Transfer Complexes, Academic Press, New York (1969).
M. Tamres and J. Yarwood: Spectroscopy and Structure of Molecular Complexes, Plenum Press, New York (1974) Ch. 3.
R. M. Izatt, J. S. Bradshaw, K. Pawlak, R. L. Bruening, and B. J. Tarbet: Chem. Rev. 92, 1261 (1992).
H. P. Hopkins, D. V. Jahagirdar, and F. J. Windler: J. Phys. Chem. 82, 1254 (1978).
J. L. Pierre, H. Handel, P. Labbe, and R. Legoaller: J. Am. Chem. Soc. 102, 6574 (1980).
A. Semnani and M. Shamsipur: J. Chem. Soc., Dalton Trans. 2215 (1996).
L. J. Andrews and R. M. Keefer: J. Org. Chem. 52, 2690 (1987).
Yu. A. Serguchev, A. B. Khotkevich, V. N. Kalinin, and V. M. Timoshenko: Teor. Ex. Chem. (Engl. Transl.) 24, 716 (1988).
E. M. Nour and L. A. Shahada: Spectrochim. Acta 44A, 1277 (1988).
E. M. Nour, L. A. Shahada, and S. S. Alkaabi: Bull. Soc. Chim. Fr. 727 (1989).
W. Hirsch, J. Greenman, and R. Pizer: Can. J. Chem. 71, 134 (1993).
A. Semnani and M. Shamsipur: J. Incl. Phenom. 22, 99 (1995).
A. Semnani and M. Shamsipur: Polish J. Chem. 71, 134 (1997)
S. Sadeghi, M. Shamsipur, and M. Elahi: Polish J. Chem. 71, 1594 (1997).
J. Zolgharnein and M. Shamsipur: Polish J. Chem. 72, 2486 (1998).
P. Labbe, R. Legoaller, H. Handel, G. Pierre, and J. L. Pierre: Electrochim. Acta 27, 257 (1982).
W. Likussar and D. F. Boltz: Anal. Chem. 43, 443 (1971).
R. S. Mulliken: J. Am. Chem. Soc. 74, 811 (1952).
E. M. Abd-Alla: Can. J. Appl. Spectrosc. 38, 88 (1993).
V. A. Nicely and J. L. Dye: J. Chem. Educ. 48, 443 (1971).
D. J. Leggett (ed.): Computational Methods for the Determination of Formation Constants, Plenum Press, New York (1985).
A. Rouhollahi, A. Kakanejadifard, S. M. F. Farnia, and M. Shamsipur: Polish J. Chem. 71, 731 (1997).
S. H. Lin, K. P. Lin, and H. Eyring: in Physical Chemistry; An Advanced Treatise, (eds. H. Eyring, D. Handerson, and W. Yost), Vol. vii, Academic Press, New York (1971), p. 1.
J. Muchova and V. Holba: Collect. Czech. Chem. Commun. 48, 1158 (1983).
F. Eggers, T. Funck, K. H. Richmann, H. Schneider, E. M. Eyring, and S. Petrucci: J. Phys. Chem. 91, 1961 (1987).
T. Tanaka, T. Hida, S. Funahashi, and M. Tanaka: J. Am. Chem. Soc. 113, 1259 (1991).
H. J. Brugge, D. Carboo, K. von Deuten, A. Knochel, J. Kopf, and W. Dreissing: J. Am. Chem. Soc. 108, 107 (1986).
J. Burgess: Ions in Solution: Basic Principles of Chemical Interactions, Ellis Horwood, Chickester (1988).
J. Ghasemi and M. Shamsipur: Polyhedron 15, 923 (1996).
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Zolgharnein, J., Shamsipur, M. Stoichiometry, Thermodynamics and Kinetics of Host–Guest Interactions between Cryptand C222 and Iodine in 1,2-Dichloroethane. Formation of a C222.I+ Inclusion Cryptate. Journal of Inclusion Phenomena 37, 395–406 (2000). https://doi.org/10.1023/A:1008127316130
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DOI: https://doi.org/10.1023/A:1008127316130