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Oxidation of Hydrocarbons Catalyzed by mu-Oxopolynuclear Mixed Metal Complexes

mu-氧多核混合金属配合物催化碳氢化合物的氧化

基本信息

批准号：
02650586
负责人：
KANAI Hiroyoshi
金额：
$ 1.15万
依托单位：
Kyoto Prefectural University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1991
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02650586/
关键词：
Polynuclear metal complexes oxidation mixed valence mixed metal complexes mu-oxo oxidative dehydrogenation carbon monooxide oxidation オキソ酸素酸化反応 μーオキソ

项目摘要

(1) The oxidation of styrene has been carried out in O_2 atmosphere with mu-oxotrinuclear ironcarboxylates, [Fe_3O(O_2CR)_6(H_2O)_3]^+. Small differences were found for oxidation rates among complexes which were dissolved in styrene. Relatively high epoxide selectivity was obtained for complexes with carboxylates, their acid strength(pKa) of nearly 4. Benzoate ligands whose Hammett values are from small negative figures to zero gave maximum epoxide selectivity(28%). (2) In the oxidation with mu-oxotrinuclear mixed valence metal carboxylates Fe_2^<III>Fe^<II> and Co_2^<III>Co^<II> are superior in the oxidation rates and epoxide selectivity to their homovalence complexes. Its homologue, V_2^<IV>V^<III> is also effective. However, Mn_2^<III>Mn^<II> has none of effectiveness. Among mixed metal (Fe_2^<III>M^<II>, M = Mn, Co, Ni, Zn, Mg) acetate complexes zinc exerted highest epoxide selectivity(35% at 85ﾟC). No activity was observed for Fe_2^<III>Mn^<II> complex. Almost the same epoxide sel … More ectivity with that for Fe_2III^<Zn>II^< was found for Cr_2>IIIFe^<II> complex. (3) The oxidation was slow at room temperature and requires higher than 70ﾟC. The oxidation rate increases with the increase of temperature and reaches maximum at 95ﾟC. Differences of activity and epoxide selectivity are observed among complexes at low temperatures but were leveled off above 95ﾟC. Highest epoxide selectivity was found at 85-95ﾟC. The decrease of oxygen pressure decreased oxidation rate, but increased epoxide selectivity. Higher than 50% of epoxide was obtained at less than 13 kPa of O_2 pressure. (4) Clustered metal oxide catalysts(Fe loading 7.8 wt%) with 3 metals were prepared by impregnating Fe_2^<III>M^<II>O(OAc)_6(H_2O)_3 (M = Fe, Mg, Zn, Mn, Co, Ni) on SiO_2 followed by calcination. Dehydrogenation of 1-butane to butadiene at 573K were carried out with those catalysts; higher activities than that for M = Fe were obtained for M = Mn and Zn, almost the same for M = Co and Ni, and no activity was observed for M = Mg. Selectivities to butadiene are 71%(Zn), 68%(Fe), 67%(Co) and 53%(Ni). Less

(1)在O_2气氛中，以多氧三核铁羧酸盐[Fe_3O(O_2CR)_6(H_2O)_3]^+为催化剂进行了苯乙烯的氧化反应。不同溶于苯乙烯的络合物的氧化速率略有不同。具有羧酸盐的配合物具有较高的环氧化物选择性，其酸强度(PKa)接近4。Hammett值从小负数到零的苯甲酸酯配体具有最高的环氧化物选择性(28%)。(2)在多氧三核混价金属羧酸盐的氧化反应中，Fe_2^&lt；III&gt；Fe^&lt；II&gt；和Co_2^&lt；III&gt；Co^&lt；II&gt；其同系物V_2^&lt；IV&gt；V^&lt；III&gt；也有效。而Mn2^lt；III&gt；Mn2^lt；II&gt；在混合金属(Fe2^&lt；III&gt；M^&lt；II&gt；，M=Mn，Co，Ni，Zn，Mg)中，锌具有最高的环氧化物选择性(85ﾟC时为35%)。Fe_2^&lt；III&gt；Mn^&lt；II&gt；络合物没有活性。几乎相同的环氧化物SEL…Cr2&Gt；IIIife；&lt；II&gt；络合物的活性比Fe_2III^&lt；Zn&gt；II^&lt；(3)常温下氧化较慢，需高于70ﾟC，氧化速率随温度升高而增加，在95ﾟC时达到最大值，低温下各络合物的活性和环氧化物选择性有所不同，但在95ﾟC以上时活性和环氧化物选择性趋于稳定，最高的环氧化物选择性在85~95ﾟC时达到最高值。在氧分压低于13kPa的条件下，可得到50%以上的环氧化物。(4)将Fe_2~+、Fe~(2+)、Al~(3+)、Al~(3+)、Gt~(3+)、Fe~(2+)、Al~(2+)、O(OAc)_6(H_2O)_3(M=Fe、Mg、Zn、Mn、Co、Ni)浸渍于SiO_2上，经焙烧后制得Fe_2~+、Fe~(2+)、Fe~(2+)、Al~(2+)、Al~(3+)、Al~(2+)、Al~(3+)、Al~(3+)、Al~(2+)、Al~(3+)、Al~(2+)、Al~(2+)、Al~(2+在573K下对正丁烷脱氢制丁二烯的反应进行了研究，发现在M=Fe和M=Mn催化剂上活性高于M=Fe，在M=Co和Ni催化剂上几乎相同，在M=Mg催化剂上无活性。对丁二烯的选择性分别为：锌71%，铁68%，钴67%，镍53%。较少