Spectroscopic Studies on Charge-Transfer Complexation of Iodine with Dibenzo-15-crown-5 and Benzo-12-crown-4 in Chloroform, Dichloromethane and 1,2-Dichloroethane

Journal of the Iranian Chemical Research

مقاله 5، دوره 5، شماره 2، شهریور 2012، صفحه 93-101   

نویسندگان

Nina Alizadeh^{* 1}؛ Mojtaba Shamsipur²

¹Department of Chemistry, University of Guilan, Rasht, Iran

²Department of Chemistry, Razi University, Kermanshah, Iran

چکیده

The formation of charge-transfer complexation between dibenzo-15-crown-5 (DB15C5) and benzo-12-
crown-4 (B12C4) (Donor) and iodine is investigated spectrophotometrically in three chlorinated solvents,
chloroform, dichloromethane (DCM) and 1,2-dichloroethane (DCE) solution at 25°C. The change in polarity
of the solvent also doesn’t affect the stoichiometry of the complexes. Values of formation constants reflect
the order of ionization potentials of the donors. The observed time dependence of the charge-transfer band
and subsequent formation of I3- ion are related to the slow formation of the initially formed 1:1 Donor.I2
outer complex to an inner electron donor-acceptor (EDAr) complex, followed by fast reaction of the inner
complex with iodine to form a triiodide ion, as follows:
Donor + I2 → Donor. I2 (outer complex), fast
Donor.I2 (outer complex) → (Donor. I+)I- (inner complex), slow
(Donor . I+)I- (inner complex) + I2 → (Donor .I+)I3-, fast
The pseudo-first-order rate constants for the transformation process were evaluated in different solvent
systems. The stability constants of the resulting EDAr complexes were also evaluated and the solvent effect
on their stability are discussed. The resulting complexes were isolated and characterized by FTIR and 1HNMR
spectroscopy.

کلیدواژه‌ها

Charge-transfer complex؛ Iodine؛ Dibenzo-15-crown-5؛ benzo-12-crown-4؛ Kinetics؛ Formation constant؛ Spectrophotometry؛ FTIR؛ 1H-NMR

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