129I Moessbauer spectroscopic study of several n-.SIGMA. charge-transfer complexes of iodine with thioethers.
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概要
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<SUP>129</SUP>I Mössbauer studies have been made of n-σ charge-transfer complexes of iodine with thioethers, such as thiane, 1,4-oxathiane, and 1,4-dithiane. The spectra of these complexes consist of two sets of quadrupole octets, corresponding to the bridging and terminal iodine atoms. The transferred charges from the thioethers are localized on the terminal iodine atoms, and the bridging iodine atoms have slightly positive charges. This result can be well explained in terms of a covalent bond between the sulfur and bridging iodine atoms or the MO treatment of a delocalized three-center four-electron bonding. The contributions of the dative structure to the ground state are estimated to be 36, 28, and 24% for thiane–iodine, 1,4-oxathiane–iodine, and 1,4-dithiane-iodine respectively. The nature of the charge-transfer bond is discussed in comparison with amine-iodine complexes.
- 公益社団法人 日本化学会の論文
著者
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Matsuyama Tomochika
Research Reactor Institute Kyoto University
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Maeda Yutaka
Research Reactor Institute Kyoto University
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Sakai Hiroshi
Research Reactor Institute Kyoto University
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