Activation of metal halide cluster and application as catalyst

金属卤化物簇的活化及其催化剂应用

• 批准号: 12640577
• 负责人: CHIHARA Teiji
• 金额: $ 2.3万
• 依托单位: The Institute of Physical and Chemical Research (RIKEN)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640577/
• 关键词: Halide cluster; Catalysis; Molybdenum halide; Niobium chloride; Brensted acid; Hydroxo complex; Olefin isomerization; Dehydrohalogenation; 芳香環メチル化; 芳香環アルキル異性化; 脱水素; ニオブ; モリブデン; レニウム; クラスターハライド; 脱水; タングステン; オレフィン; 水素化; 異性化; 分解反応; ニオブクラ

Application of halide clusters of Nb, Ta ([(M_6Cl1_2)Cl_2(H_2O)_4]・4H_2O(M=Nb,Ta)),Mo,W(((H_3O)_2[(M_6Cl_8)Cl_6]・6H_2O(M =Mo,W)), and Re([Re_3Cl_9]) as catalysts was made in a gas flow reactor under a hydrogen or helium stream. When the halide cluster was treated above 150℃, evolution of hydrogen chloride was deteced. Above this temperature, decomposition of phenyl acetate to phenol and ketene, dehydration of alcohol to olefin or ether, isomerization of olefinic double bond, and dehydrohalogenation of halogenated alkane proceeded over halide cluster catalyst. Thus, a novel research area of halide cluster catalysis was initiated after 143 years of the first report for the synthesis of molybdenum chloride. These reactions are catalyzed by conventional solid acid catalysts. Analyses of adsorbed pyridine over the activated cluster catalyst showed the presence of Brensted acid site, which would be attributable to the hydroxo ligand such as [(Mo_6Cl_8)Cl_4(OH_2)(OH)].Dehydrogenation and dealkylation, which are catalyzed by platinum group metals, and polymerization, which is catalyzed by group 4 transition metal compounds, are revealed to be catalyzed by halide cluster. We are planning to study the scope and limitations of halide cluster catalysis and to develop unique reaction that is catalyzed by halide cluster. The goal of this study is to construct a new research area of "halide cluster catalysis."

在氢气或氦气流下的气流反应器中，应用Nb、Ta ([(m_6cl12)Cl_2（H_2O)_4]·4H_2O(M=Nb,Ta)）、Mo、W(((H_3O)_2[（m_6cl8)Cl_6]·6H_2O(M =Mo，W)）和Re（[re_3cl9]）卤化物簇作为催化剂。当卤化物团簇温度高于150℃时，检测到氯化氢的析出。在此温度以上，乙酸苯酯分解为苯酚和烯酮，醇脱水为烯烃或醚，烯烃双键异构化，卤化烷烃脱氢卤化在卤化物团簇催化剂上进行。至此，继143年来首次报道氯化钼的合成后，开启了卤化物团簇催化的新研究领域。这些反应是由传统的固体酸催化剂催化的。对活化团簇催化剂上吸附的吡啶的分析表明，Brensted酸位点的存在可能是由于羟基配体[(Mo_6Cl_8)Cl_4(OH_2)(OH)]。铂族金属催化的脱氢和脱烷基反应和第4族过渡金属化合物催化的聚合反应均由卤化物团簇催化。我们计划研究卤化物团簇催化的范围和局限性，并开发由卤化物团簇催化的独特反应。本研究旨在构建一个新的“卤化物团簇催化”研究领域。

项目成果

Satoshi Kamiguchi, Teiji Chihara, et al.: "Catalytic Isomerization of 1-Hexene to 2-Hexenes by Halide Clusters of Nb, Mo, Ta and W Possessing an Octahedral Metal Core"J.Mol.Catal.A. (in press).

Satoshi Kamiguchi、Teiji Chihara 等人：“通过拥有八面体金属核的 Nb、Mo、Ta 和 W 卤化物簇将 1-己烯催化异构化为 2-己烯”J.Mol.Catal.A.

Satoshi Kamiguchi, Teiji Chihara, et al.: "Catalytic Isomerization of 1-Hexene to 2-Hexenes by Halide Clusters of Nb, Mo, Ta, and W Possessing an Octahedral Metal Core"J.Mol.Catal.A. 195. 159-171 (2003)

Satoshi Kamiguchi、Teiji Chihara 等人：“通过拥有八面体金属核的 Nb、Mo、Ta 和 W 卤化物簇将 1-己烯催化异构化为 2-己烯”J.Mol.Catal.A.

S.Kamiguchi: "Synthesis and Structure of a Molybdenum-Cobalt Bimetallic Carbide Cluster[N(PPh3)2][Mo3Co3(μ6-C)(μCO)3(CO)15]..."J.Cluster Sci.. 11・4. 483-492 (2000)

S.Kamiguchi：“钼钴双金属碳化物簇的合成与结构[N(PPh3)2][Mo3Co3(μ6-C)(μCO)3(CO)15]...”J.Cluster Sci.. 11・4。483-492（2000）

Teiji Chihara, Satoshi Kamiguchi: "Catalytic Decomposition of Phenyl Acetate by Halide Clusters of Nb, Mo, Ta, and W Possessing an Octahedral Metal Core"Chem.Lett.. 70-71 (2002)

Teiji Chihara、Satoshi Kamiguchi：“具有八面体金属核的 Nb、Mo、Ta 和 W 卤化物簇催化乙酸苯酯的分解”Chem.Lett.. 70-71 (2002)

H.Ogawa: "Selective cyclization of 6-aminocapric acid adsorbedin silica gel toε-caprolactam : IR analysis of adsorbedsate"J.Phys.Org.Chem.. 14・1. 52-57 (2001)

H.小川：“吸附在硅胶上的6-氨基癸酸选择性环化为ε-己内酰胺：吸附物的IR分析”J.Phys.Org.Chem.. 14・1(2001)。