Activation of metal halide cluster and application as catalyst

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））和Re（[Re_3Cl_9]）是在氢气流或氦流下合成气体流反应器。当卤化物簇在150 ° C以上被治疗时，氢氯化物的演变也被发现。在此温度上，苯乙酸酯到苯醇和酮的分解，酒精醇到olefin或ether的脱水，烯烃双键的异构化，以及通过卤化物簇催化剂进行的卤素烷的脱氢化。Thus，一个新的卤化物簇催化研究区域在143年后启动了第一份关于氯化分子合成的报告。这些反应是由传统的固体酸催化剂分类的。对活跃集群催化剂上吸附的吡啶进行分析显示Brensted酸位点的存在，将对羟基配体的影响作为[（Mo_6Cl_8）Cl_4（OH_2）（OH）]。脱水和降解，由铂族金属催化，由聚合物催化，由第4组过渡金属化合物催化，被揭示为由卤化物簇催化。我们正在计划研究卤化物簇催化的范围和限制，并开发一种由卤化物簇催化的独特反应。此study is to construct a new res\area of "halide cluster cat\sis。"

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."