Abstract
Interactions of hexaaza-18-crown-6 (HA18C6) and tetraaza-14-crown-4 (TA14C4) with iodine have been investigated spectrophotometrically in chloroform solution. The observed time dependence of the charge-transfer band and subsequent formation of I3 - in solution were related to the slow transformation of the initially formed 1:1 macrocycle. I2 outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion, as follows:
macrocycle + I2→fast K f macrocycle.I2 (outer complex)
macrocycle.I2 (outer complex) →slow (macrocycle.I+)I- (inner complex)
macrocycle.I+)I- (inner complex) + I2→slow (macrocycle.I+)I3 -.
The pseudo-first-order rate constants at various temperatures for thetransformation process were evaluated from the absorbance-time data. The activation parameters (Ea, Δ H‡, and Δ S‡) for thetransformation were obtained from the temperature dependence of the rate constants. The stoichiometry and formation constants of the resulting EDA complexes have also been determined. It was found that the (TA14C4.I+)I3 - is more stable the (HA18C6.I+)I3 - complex in chloroform solution.
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References
A.M. Slifkin: Charge Transfer Interaction of Biomolecules, Academic Press, New York (1971).
B. Pullman: Molecular Association in Biology, Academic Press, New York (1968); K.A. Connors: Binding Constants, Wiley, New York (1987).
C.J. Pedersen: J. Am. Chem. Soc. 89, 7017 (1967).
R.M. Izatt, J.J. Bradshow, K. Pawalk, and R.L. Bruning: Chem. Rev. 91, 1721 (1991).
E. Shchori, J. Jagur-Grodzinski, Z. Lus, and M. Shporer: J. Am. Chem. Soc. 93, 7133 (1971).
H.P. Hopkins, Jr., D.V. Jahagirdar, and F.J. Windler: J. Phys. Chem. 82, 1254 (1978).
L.J. Andrews and R.M. Keefer: J. Org. Chem. 52, 2690 (1987).
A.E. Mourad: Bull. Pol. Acad. Sci. Chem. 33, 483 (1986).
R. Le Goaller, H. Handel, P. Labbe, and J.L. Pierre: J. Am. Chem. Soc. 106, 1694 (1984).
E.M. Nour and L.A. Shahada: Spectrochim. Acta 44A, 1277 (1988).
N.S. Rao, G.-B. Rao, and D. Ziessow: Spectrochim. Acta. 46A, 1107 (1990).
E.M. Nour: Spectrochim. Acta 47A, 1277 (1991).
A. Semnani and M. Shamsipur: Spectrochim. Acta 49A, 411 (1993).
A. Semnani and M. Shamsipur: J. Incl. Phenom. 22, 99 (1995).
A. Semnani and M. Shamsipur: J. Chem. Soc. Dalton Trans 2215 (1996).
M. Hasani and M. Shamsipur: J. Incl. Phenom. 28, 32 (1997).
A. Semnani and M. Shamsipur: Pol. J. Chem. 71, 134 (1997).
R.P. Lang: J. Am. Chem. Soc. 84, 1185 (1962).
P.C. Dwivedi: Curr. Sci. 39, 107 (1970).
J.M. Daisey and A.J. Sonnessa: J. Phys. Chem. 76, 1895 (1972).
K.R. Bhaskar, S.N. Bhat, S. Singh, and C.N.R. Rao: J. Inorg. Nucl. Chem. 28, 1915 (1966).
V.G. Krishna and M. Chowdhury: J. Phys. Chem. 67, 1067 (1963).
D.C. Mukherjee and A.K. Chandara: J. Phys. Chem. 68, 477 (1964).
G. Aloisi, G. Cauzzo, and U. Mazzucato: Trans. Faraday Soc. 61, 1406 (1965).
R.S. Mulliken and W.B. Person: Molecular Complexes, Wiley, New York (1969).
M. Tawres and J. Yarwood: Spectroscopy and Structure of Molecular Complexes, Plenum, New York (1974).
E.M. Nour: Spectrochim. Acta 47A, 473 (1991).
S. Sadeghi and M. Shamsipur: Polish J. Chem. 71, 1594 (1997).
J. Zolgharnein and M. Shamsipur: Polish J. Chem. 72, 2486 (1998).
M. Mizumno, J. Tanaka, and I. Harada: J. Phys. Chem. 85, 1789 (1981).
M. Ciureanu and V.E. Sahini: Rev. Roum. Chim. 22, 1441 (1977).
N.S. Rao, G.B. Rao, and D. Ziessov: Spectrochim. Acta 46A, 1107 (1980).
S.H. Lin, K.P. Li, and H. Eyring: in H. Eyring, D. Handerson and W. Yost (eds), Physical Chemistry, an Advanced Treatise, Academic Press, New York, Vol. II (1977) p. 1.
A.A. Frost and R.G. Pearson: Kinetics and Mechanism, 2nd ed, Wiley, New York, (1963) p. 135.
W. Likussar and D.F. Boltz: Anal. Chem. 43, 1262 (1971).
S. Itoh, J. Maruta, and S. Fukuzumi: J. Chem. Soc., Perkin Trans. 2 1429 (1996).
V.A. Nicely and J.L. Dye: J. Chem. Educ. 48, 443 (1971).
M.J. Bovill, D.J. Chadwick, and I.O. Sutherl: J. Chem. Soc., Perkin Trans. 2 1529 (1980).
J.D. Dunitz and P. Seiler: Acta Crystallogr. 30B, 2739 (1974).
P. Labbe, E. Le Goaller, H. Handel, G. Pierre, and J.L. Pierre: Electrochim. Acta 27, 257 (1982).
C.J. Pedersen: J. Am. Chem. Soc. 92, 386 (1970).
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Hasani, M., Shamsipur, M. Interaction of Iodine with Hexaaza-18-crown-6 and Tetraaza-14-crown-4 in Chloroform Solution. Journal of Inclusion Phenomena 48, 135–139 (2004). https://doi.org/10.1023/B:JIPH.0000022520.53138.f4
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DOI: https://doi.org/10.1023/B:JIPH.0000022520.53138.f4