Synthesis and coordination behaviors of new double-sided porphyrinatoiron(II) complexes: Effect of the pocket-size for imidazole on dioxygen binding.
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概要
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The synthesis and characteristic ligation behaviors of new "double-sided porphyrinatoiron(II) complexes" having two pockets of different spacing-size on each side of a ring plane and a larger sized one on both sides of a macrocycle, are described. The equilibrium constants for the imidazole derivatives to the four-coordinated porphyrinatoiron(II)s were increased in proportion to the size of the pocket-space, which is reflected by the <I>ΔH</I> term. The five-coordinated complexes of the porphyrinatoirons, obtained by the addition of 1,2-dimethyl-imidazole (1,2-dmin) in a toluene solution, formed stable and reversible dioxygen adducts at 25°C. The oxygen affinities for the iron(II) complexes increased as the steric bulk on the rear side of the porphyrin plane was relieved. These changes in the oxygen affinity are attributed to the strength of the π-electron donation from the imidazole to the central iron ion.
- 公益社団法人 日本化学会の論文
著者
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Nakao Keisuke
Department Of Otorhinolaryngology Fukuoka Municipal Hospital For Children
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Nishide Hiroyuki
Department Of Applied Chemistry Waseda University
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Tsuchida Eishun
Department Of Applied Chemistry Waseda University
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Komatsu Teruyuki
Department Of Applied Chemistry Faculty Of Science And Engineering Chuo University
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Hasegawa Etsuo
Department of Polymer Chemistry, Waseda University
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Hasegawa Etsuo
Department of Applied Chemistry, Waseda University
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Nakao Keisuke
Department of Polymer Chemistry, Waseda University
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Nakata Taisaku
Department of Polymer Chemistry, Waseda University
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