Synthesis of Manganese Oxide Clusters with Oxidation Catalysis

氧化催化合成锰氧化物团簇

• 批准号: 11640569
• 负责人: ISOBE Kiyoshi
• 金额: $ 2.3万
• 依托单位: Osaka City University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640569/
• 关键词: oxidation catalysis; oxometalate; tacn complex; Cp^*Rh-W oxide cluster; ESI-mass spectrometer; windmill type; triple cubane type; sprayer for measurement of short live species; 立方体型(tacn)Mn-Mo系クラスター; 金属酸化物複合体

We synthesized Mn-Mo and Rh-W oxide clusters with tacn (1,4,7-triazacyclononane) derivatives and Cp (cyclopentadienyl) ligands, respectively. Their ability of oxidation catalysis for hydrocarbon compounds was examined.A reaction of the dinuclear oxometalate of [(n-Bu_4)N]_2[Mo_2O_7] and (tacn) MnCl_3 in water afforded a new cubic type of the Mn-Mo mixed metal oxide cluster of [{(tacn)Mn}_2Mo_4O_<16>]-4H_2O (1). An X-ray analysis of 1 reveals that it is composed of a cubic framework consisting of one Mn(IV), three Mo (VI) ions and four oxygen atoms. It also has an incomplete cubic framework formed by three Mo (VI) ions and four oxygen atoms.We examined catalytic ability of 1 towards the bleaching of pinacyanol chloride dye (PC dye). In the reaction using 1 the blue color of the dye disappeared in 6h in water under heterogeneous conditions : hydrogen peroxide (15 mol), PC dye (15 mol) and catalyst (1.5 mol). This preliminaly results show that cluster 1 is able to use a mild bleaching catalyst for a heterogeneous system.Rh-W oxide clusters with the Cp^* ligand were prepared in two geometrical isomers of [(Cp^*Rh)_4W_4O_<16>] from the reaction of the mononuclear [WO_4]^<2-> with [Cp^*RhCl(μ-Cl)]_2 in CH_3CN : two geometrical isomers have a windmill and a triple cubane geometrical framework. The former was formed selectively below 20℃. Above 60℃ the latter was obtained specifically in the same reaction system. We studied the mechanisms for the isomerization and the formation of those isomers by using ^<17>O NMR spectroscopy and ESI-MS.It is found that a species with a ladder structure plays an important role for both the isomerization and the formation of the isomers.

我们分别以TACN(1，4，7-三氮杂环烷)衍生物和Cp(环戊二烯)为配体合成了Mn-Mo和Rh-W氧化物簇合物。[(n-Bu_4)N]_2[Mo_2O_7]与(Tacn)MnCl3在水中反应生成了一种新的立方结构的锰-钼混合金属氧化物簇合物[(Tacn)Mn}_2Mo_4O&lt；16&gt；]-4H2O(1)。1的X-射线分析表明，它是由1个Mn(IV)，3个Mo(VI)离子和4个氧原子组成的立方骨架。它还具有由三个Mo(VI)离子和四个氧原子组成的不完全立方骨架。我们考察了1对氯化Pinacyol染料(PC染料)漂白的催化能力。在非均相条件下，在过氧化氢(15mol)、PC染料(15mol)和催化剂(1.5mol)的作用下，染料的蓝色在水中6h内消失。这一初步结果表明，簇合物1能够在非均相体系中用作温和的漂白催化剂。[(Cp^*Rh)_4W_4O_&lt；16&gt；]的两个几何异构体与[Cp^*Rh)_4W_4O_&lt；16&gt；]在CH3CN中与[Cp^*RhCl(μ-Cl)]_2反应生成了具有Cp^*配体的Rh-W氧化物簇合物：两个几何异构体分别具有风车和三方几何骨架。前者选择性地在20℃以下形成。在60℃以上，后者是在同一反应体系中得到的。用核磁共振波谱和ESI-MS研究了异构化反应和异构体的形成机理，发现具有梯形结构的物种对异构化和异构体的形成都起着重要作用。

项目成果

Kentaro Kimura, Takahiro Kimura, Isamu Kinoshita, Nobuaki Nakashima, Ken'ichi Kitano, Takanori Nishioka, Kiyoshi Isobe: "Aerobic Oxidation of a Disulfide to its Sulfonate Leading to Supramolecular Pyridine-2-sulfonato Cu(II) and Zn(II) Complexes"Chem.Comm

Kentaro Kimura、Takahiro Kimura、Isamu Kinoshita、Nobuaki Nakashima、Kenichi Kitano、Takanori Nishioka、Kiyoshi Isobe：“二硫化物有氧氧化为其磺酸盐，生成超分子吡啶-2-磺酸根 Cu(II) 和 Zn(II) 配合物

Rimo Xi, Bateer Wang, Masaaki Abe, Yoshiki Ozawa, Isamu Kinoshita, and Kiyoshi Isobe: "Tetranuclear Mo2Rh2 Complexes Obtained from Reactions between Triple Cubane-type Oxide Cluster [(Cp^*Rh)4Mo4O16] (Cp^*=η5-C5(CH3)5) and Methanethiol"Bull.Chem.Soc.Jpn..

Rimo Xi、Bateer Wang、Masaaki Abe、Yoshiki Ozawa、Isamu Kinoshita 和 Kiyoshi Isobe：“从三重古巴烷型氧化物簇 [(Cp^*Rh)4Mo4O16] 之间的反应获得四核 Mo2Rh2 配合物 (Cp^*=η5-C5) (CH3)5) 和甲硫醇“Bull.Chem.Soc.Jpn..

Kenichi Kitano,Rika Tanaka,Takahiro Kimura,Toshiyuki Tsuda,Seiji Shimizu,Hideaki Takagi,Takanori Nishioka,Daisuke Shimoi,Akio Ichimura,Isamu Kinoshita,Kiyoshi Isobe,and Shun ichiro Ooi: "Lantern-type Dinuclear CrIIIPtII and VIVPtII Complexes Bridged by Py

Kenichi Kitano、Rika Tanaka、Takahiro Kimura、Toshiyuki Tsuda、Seiji Shimizu、Hideaki Takagi、Takanori Nishioka、Daisuke Shimoi、Akio Ichimura、Isamu Kinoshita、Kiyoshi Isobe 和 Shun ichiro Ooi：“Py 桥接的灯笼型双核 CrIIIPtI​​I 和 VIVPtII 配合物

Koji Nishikawa, Isamu Kinoshita, Takanori Nishioka, and Kiyoshi Isobe: "Synthesis and X-Ray Analysis of Mn-Mo Mixed Metal Oxide Cluster with Cubic Framework"Chem.Lett.. 1342-1343 (2000)

Koji Nishikawa、Isamu Kinoshita、Takanori Nishioka 和 Kiyoshi Isobe：“具有立方骨架的 Mn-Mo 混合金属氧化物簇的合成和 X 射线分析”Chem.Lett.. 1342-1343 (2000)

Koji Nishikawa,Isamu Kinoshita,Takanori Nishioka,and Kiyoshi Isobe: "Synthesis and X-Ray Analysis of Mn-Mo Mixed Metal Oxide Cluster with Cubic Framework"Chem.Lett.. 1342-1343 (2000)

Koji Nishikawa、Isamu Kinoshita、Takanori Nishioka 和 Kiyoshi Isobe：“具有立方骨架的 Mn-Mo 混合金属氧化物簇的合成和 X 射线分析”Chem.Lett.. 1342-1343 (2000)