Synthesis and Molecular Design of Novel Modified-Heteropolyanions Containing Multicenter Active Sites
Synthesis and Molecular Design of Novel Modified-Heteropolyanions Containing Multicenter Active Sites
批准号:
10640552
负责人:
NOMIYA Kenji
金额:
$1.98万
依托单位:
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (C)
财政年份:
1998
资助国家:
日本
项目状态:
已结题
起止时间:
1998 至 2000
中文摘要
本研究取得了以下几个新成果:1。在1,4,9 -三钒(V)取代Keggin多氧钨酸盐[1,4,9 - pw_9v_3o_ <40>]^<6->的V_3表面(b位)上合成了Cp^*Rh^<2+>配合物(Cp^* = C_5Me_5)。产物中还含有[Cp^*Rh(DMSO)_3]^<2+>。分离得到了三ti ^<IV>和二ti ^<IV>取代Keggin多氧钨酸盐,并测定了它们的x射线晶体结构。在水溶液中进行了超离心分子量(MW)测量。两种Ti^<IV>-取代物均为二聚体,分别为两种α-Keggin [1,2,3 - pw_9ti_3o_ <40>]^<9->单元和两种新型α-Keggin [1,2 - pw_ <10>Ti_2O_<40>]^<7->单元的Ti- o -Ti酸酐形式。溶液分子量测定表明,前者在pH7.0水溶液中为二聚体,后者在ph7.8水溶液中为单体。合成了三金属取代的Dawson多氧钨酸盐[P_2W_<15>M_3O_<62>]^<9-> (M = Nb^V, V^V)与有机金属基团((cod)Pt^<2+>和Cp^*Rh^<2+>)之间的负载型多氧钨酸盐,并阐明了多氧阴离子载体(Nb vs. V)和有机金属基团((cod)Pt^<2+> vs. Cp^*Rh^<2+>)的影响。采用GC/MS分析了几种钒(V)取代的Keggin和Dawson多金属氧酸盐在30% H_2O_2水溶液中催化甲苯和硝基苯的氧化产物。对通过离子机制和自由基机制促进反应的多金属氧酸盐进行了分类。
英文摘要
Several novel results in this research were obtained :1. The Cp^*Rh^<2+> complex (Cp^* = C_5Me_5) supported on the V_3 surface (B-site) of 1, 4, 9-tri-vanadium(V)-substituted Keggin polyoxotungstate [1, 4, 9-PW_9V_3O_<40>]^<6-> was synthesized. The product also contained [Cp^*Rh(DMSO)_3]^<2+> as counterion.2.Tri-Ti^<IV>-and di-Ti^<IV>-substituted Keggin polyoxotungstate were isolated as potassium salts and their X-ray crystal structures determined. Ultracentrifugation molecular weight (MW) measurements were also performed in aqueous solution. The two Ti^<IV>-substituted compounds in the solid state were dimeric, Ti-O-Ti anhydride forms of two α-Keggin [1, 2, 3-PW_9Ti_3O_<40>]^<9-> units and of two novel α-Keggin [1, 2-PW_<10>Ti_2O_<40>]^<7-> units, respectively. Solution MW measurements showed that the former was a dimer in pH7.0 aqueous solution, whereas the latter was a monomer in pH 7.8 aqueous solution.3. The supported-polyoxotungstates formed between tri-metal-substituted Dawson polyoxotungstate [P_2W_<15>M_3O_<62>]^<9-> (M = Nb^V, V^V) and organometallic groups ((cod)Pt^<2+> and Cp^*Rh^<2+>) were synthesized, and the effects polyoxoanion-support (Nb vs. V) and organometallic species ((cod)Pt^<2+> vs. Cp^*Rh^<2+>) were elucidated.4. Oxidation products of toluene and nitrobenzene with 30% aqueous H_2O_2 catalyzed by several vanadium(V)-substituted Keggin and Dawson polyoxometalates were carefully analyzed by GC/MS measurements. Polyoxometalates which promote the reaction via an ionic mechanism and via a radical mechanism were classified.
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K.Nomiya et al.: "Active sites of vanadium-substituted POM catalysts on benzene hydroxylation"J.Mol.Catal.. A152. 55-68 (2000)
K.Nomiya 等人:“钒取代 POM 催化剂对苯羟基化的活性位点”J.Mol.Catal.. A152。
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通讯作者:
K.Nomiya et al: "Benzene hydroxylation with hydrogen peroxide catalyzed by vanadium(V)-substituted POMs"J.Mol.Catal.,2000. (in press).
K.Nomiya 等人:“钒 (V) 取代的 POM 催化的过氧化氢苯羟基化”J.Mol.Catal.,2000。
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K.Nomiya et al.: "Benzene hydroxylation catalyzed by vanadium(V)-substituted POMs"J.Mol.Catal.. A156. 143-152 (2000)
K.Nomiya 等人:“钒 (V) 取代的 POM 催化的苯羟基化”J.Mol.Catal.. A156。
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K.Nomiya et al.: "Multicenter active sites of vanadium-substituted polyoxometalate catalysts on benzene hydroxylation with hydrogen peroxide and two reaction types with and without an induction period"J.Mol.Catal.. Vol.A152. 55-68 (2000)
K.Nomiya 等人:“钒取代的多金属氧酸盐催化剂对过氧化氢苯羟基化的多中心活性位点以及有和没有诱导期的两种反应类型”J.Mol.Catal.. Vol.A152。
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K.Nomiya et al.: "Synthesis of Triniobium(V)-Substituted SiW_9Nb_3O_<40>^<7-> Heteropolyoxoanions"Bull.Chem.Soc.Jpn.. 71(11). 2603-2610 (1998)
K.Nomiya等人:“Trniobium(V)-取代的SiW_9Nb_3O_<40>^<7->杂多氧阴离子的合成”Bull.Chem.Soc.Jpn..71(11)。
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共 21 条
Design and Synthesis of Suprarmolecular Metal Complexes Under the Chemical Reaction Fields of Polyoxometalates
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Synthesis and Molecular Design of Heteropolyanion-Supported Organometallics Using Modified Heteropolyanion-Support
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负责人:NOMIYA Kenji
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