Charge-transfer Complexes between Iodine and Various Aliphatic Amines
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概要
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Mulliken's charge-transfer type molecular complexes between iodine and various aliphatic amines were studied spectrophotometrically in <I>n</I>-heptane solutions. The electron donor components used in the present study include ammonia, primary amines (methyl-, ethyl- and <I>n</I>-butyl-), secondary amines (dimethyl-, diethyl-and piperidine), and also tertiary amines (tri-methyl-, tri-<I>n</I>-propyl- and tri-<I>n</I>-butyl-). The charge-transfer absorption bands characteristic of molecular complexes of this kind appeared between 229 and 281 mμ depending on the kind of amines used as electron donors. The stable equilibria of 1:1 complex formation were verified for all the systems. The equilibrium constants (<I>K</I>) were determined at various temperatures and the heats of formation (<I>ΔH</I>) and entropy changes (<I>ΔS</I>) were evaluated. The values of <I>ΔH</I> range from －4.8 kcal./mol. for ammonia complex to －12.3 kcal./mol. for tri-<I>n</I>-butylamine complex, and <I>ΔS</I> also changes from －8.0 e. u. for the former and －27.8 e. u. for the latter. The effect of successive replacement of hydrogen atoms of ammonia by methyl or ethyl groups on the value of <I>ΔH</I> was shown to be additive. From the data of <I>ΔH</I> and <I>ΔS</I> it was concluded that there exists a linear relation between these two quantities for the iodine complexes with all the primary amines and secondary amines having rather small substituent groups like methyl. The deviation from the linear relation was observed with the complexes including diethylamine and tertiary amines as electron donors. These amines with bulky substituent groups may be expected to exert a great steric hindrance in the case of the molecular complex formation. Further it was shown that the plots of <I>ΔH</I>'s against σ<SUP>*</SUP>'s (Hammett's substituent constant) fit the straight line, except for those of the iodine complexes with triethylamine, tri-<I>n</I>-propylamine and tri-<I>n</I>-butylamine. With the aid of the spatial configuration derived from X-ray crystal analysis data for the trimethylamine-iodine complex, one could evaluate the three parameters (over-lap integral (<I>s</I>), exchange integral (β) and effective electron affinity (<I>A</I>)) which are necessary for explaining reasonably the relation between the transition energies of the charge-transfer bands and the ionization potentials of electron donors. For example, the β values thus estimated were －2.09, －2.20 and －2.32 eV. for the complexes with primary, secondary and tertiary amines, respectively.
- 社団法人 日本化学会の論文
著者
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Tanaka Jiro
The Institute For Solid State Physics The University Of Tokyo
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Nagakura Saburo
The Institute for Solid State Physics The University of Tokyo
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Yada H.
The Institute for Solid State Physics The University of Tokyo
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Yada Hiroshi
The Institute for Solid State Physics The University of Tokyo
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