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図書 |
図書
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edited by Rudi van Eldik, Leroy Cronin
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| 2.
図書 |
図書
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edited by Michael T. Pope and Achim Müller
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論文 |
論文
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3. Formation of vv lacunary polyoxovanadates and interconversion reactions of dodecavanadate species
Okaya, Kenji ; Kobayashi, Tetsuhiro ; Koyama, Yuki ; Hayashi, Yoshihito ; Isobe, Kiyoshi
概要:
金沢大学理工研究域物質化学系<br />Oxidation, reactions of the reduced decavanadate [VIV2Vv8O26]4- (1) with halide guest anions were in
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vestigated for the synthesis of Vv host molecules. The reaction with Cl- afforded a new dodecavanadate, [HVV12O32(C1)]4-(3), which incorporated the guest chloride anion. The polyoxovanadate framework of 3 is different from, the bowl-shaped dodecavanadate [VV12O 32(CH3CN)]4- (2). The structure of 3 is regarded as a trilacunary counterpart of the pentadecavanadate [V V9VIV8O36C1] 4-. Employment: of an F-template yielded the layered polyoxovanadate [HVV11O29F2] 4- (4). The framework of 4 is a monolacunary structure of the fluoride-incorporated dodecavanadate [H6VV2VIv10O30F2] 6-, in which one of the VO groups at the belt position is removed. The three vana-dium atoms in the capping units are connected, by (μ3-F bridges. Reaction with Br provided [HVv12O32(Br)]4- (5) with minor formation of [H3VV10O28]3- Interconversion reactions between 2, 3, and 4 proceeded as follows: the reaction of 2 with Cl- prompted, an isomerization reaction of the bowl-type framework, affording 3; the reaction of 3 with F- gave 4; the reaction of 4 with CH3CN reproduced acetonitrile-incorporated 2. Complexes 3 and 4 were characterized by X-ray analysis. Polyoxovanadates 3 and 4, with the highest oxidation cores, exhibited distinct signals in the 51V NMR spectra, corresponding to lacunary polyoxovanadate geometries. © Wiley-VCH Verlag GmbH & Co. KGaA.
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| 4.
論文 |
論文
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Kobayashi, Tetsuhiro ; Kuwajima, Sho ; Kurata, Taisei ; Hayashi, Yoshihito
概要:
A spherical tetradecavanadate, [V14O38(Cl)] 7-, was synthesized from a chloride-incorporated bowl-type dodecavanadate. © 2014 Elsevier B.V. All rights reserved.
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論文 |
論文
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Inami, Shinnosuke ; Nishio, Masaki ; Hayashi, Yoshihito ; Isobe, Kiyoshi ; Kameda, Hiroyuki ; Shimoda, Tatsuya
概要:
金沢大学理工研究域物質化学系<br />An all-inorganic complex, [Mn2{(CVO3) 5}2]6- (1), was synthesized, and the structure determination r
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eveals a dinuclear manganese complex coordinated by two cyclic pentavanadate ligands. The cyclic pentavanadate units sandwich the edge-sharing octahedral dimanganese core through, coordination of the oxido group of the pentavanadate. A. dinuclear cobalt complex with, a cyclic decavanadate, [Co 2(OH2)2(VO3)10]6- (2), was also synthesized. The structure analysis reveals a dinuclear cobalt complex with a macrocyclic decavanadate, which is composed of 10 VO4 units joined by the vertex. Sharings. The CoO6 octahedrons are edge-shared, with each cobalt octahedron coordinated to five oxido groups from the decavanadate. The remaining site is occupied by - water. The coordinated water molecules are supported with hydrogen bonds in two directions. Complex 2 in acetonitrile shows no reactivity with dioxygen even at low temperature, and the cyclic voltammogram of 2 shows no redox chemistry in acetonitrile. Complex 2 exhibits chromism by water exposure both, in the solid state and. in acetonitrile. Complex 2 is green-yellow in color, and. the addition of water causes the complex to turn brown. After heating the sample, it returns to its original color in a reversible manner. The EXAFS data in acetonitrile is also reported, and is consistent with the solid-state structure. © Wiley-VCH Verlag GmbH & Co. KGaA.
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