Polymer-supported trichlorotitanium(III) complexes and their dioxygen adducts.
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概要
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Various polymer-supported trichlorotitanium(III) (TiCl<SUB>3</SUB>) complexes were prepared in pyridine or THF from TiCl<SUB>3</SUB> and copolymers composed of 4-vinylpyridine (10, 20, and 65 mol%), divinylbenzene (0 and 20 mol%), and styrene. The ESR technique was employed for structural studies of titanium(III) species and their dioxygen adducts contained in the supported complexes. The supported complexes contained, as titanium(III) species, mainly (>88%) mixtures of TiCl<SUB>3</SUB>(pyr)<I><SUB>n</SUB></I>L<SUB>3−<I>n</I></SUB> (<I>n</I>=1, 2, and 3), where pyr is a pyridyl group of the supports and L is a molecule of the solvents used in preparation. The relative amounts of the species having smaller <I>n</I> values increased with cross-linking, with a decrease in the content of pyridyl groups, and with pretreatment with tetra-chlorotitanium(IV) (TiCl<SUB>4</SUB>). On exposure to oxygen the supported complexes gave two or three kinds of dioxygen adducts (Ti(IV)–O<SUB>2</SUB><SUP>−</SUP>) characterized by <I>g</I><SUB>1</SUB> the principal <I>g</I> value along the axis of O–O bond. The <I>g</I><SUB>1</SUB> values of three dioxygen adducts α, β and γ were 2.027–2.028, 2.022–2.024, and 2.017–2.018, respectively. The probable structures of α, β, and γ, when L is THF, are [TiCl<SUB>2</SUB>(pyr)<SUB>3</SUB>(O<SUB>2</SUB>)]Cl, TiCl<SUB>3</SUB>(pyr)<SUB>2</SUB>(O<SUB>2</SUB>), and TiCl<SUB>3</SUB>(pyr)L(O<SUB>2</SUB>), respectively, their precursors being the titanium(III) species having the <I>n</I> values of 3, 2, and 1, respectively.
- 公益社団法人 日本化学会の論文
著者
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Yoshida Satohiro
Department Of Hydrocarbon Chemistry And Division Of Molecular Engineering Faculty Of Engineering Kyo
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Tarama Kimio
Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University
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Chimura Yasuo
Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University
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Beppu Masazo
Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University
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