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膦化聚苯乙烯担载四核羰基钴簇的合成和催化作用

Phosphino- Polystyrene Supported Metal Carbonyl Cluster: Synthesis, Characterization and Catalysis

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【作者】 罗玉忠李红兵沈海邑傅宏祥马玉源高兰云周跃坤王继锋

【Author】 Luo Yuzhong, Li Hongbing, Shen Haiyi, Fu Hongxiang, Ma Yuyuan, Gao Lanyun(State Key Laboratory of Oxo-Symthesis and Selective Oxidation, Lanzhou Instituteof Chemical Physics, Chinese Academy of Sciences, lanzhou 730000)Zhou Yaokun, Wang Jifeng (Department of Chemistry. Lanzhou Unwersity,Lanzhou 730000)

【机构】 中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室兰州大学化学系兰州大学化学系 兰州730000兰州730000兰州730000

【摘要】 合成了两种含膦聚苯乙烯载体和此二载体与四核羰基钴簇CO4(CO)82-CO2(μ4-PPh)2通过配体交换反应,合成两种担载的金属原子簇催化剂.用IR、VU-DRS和XPS表征担载簇配合物的结构.考察了担载簇催化剂对讣茑烯烃的氢甲酰化反应的催化活性.其活性顺序为:1-庚烯>环己烯>二异丁烯>2-辛烯>苯乙烯.

【Abstract】 Two phosphino- polystyrene supported tetranuclear cobalt carbonyl metal clusterspph (n-Bu) Co4(CO)7 (μ2-CO)2 (μ4-PPh)2] (Ⅱ) and CH2PPh2 + Co4 CO)7 (μ2-CO)2 (μ4-PPh)2] ( Ⅲ ) have been synthesized. The preparation was carried out by the reactions between the tetranuclear cobalt carbonyl metal cluster Co4 (CO)8(μ2-CO)2(μ4-PPh)2 ( I ) and two phosphino-polystyrene supported polystyryibutylphenylphosphine PPh(n-Bu)(b) and (polystyrylmethyl)diphenyl phosphine CH2PPh2 (c) through ligand exchangereaction.The structures of the two phosphinopolystyrene supported tetranuclear cobalt carbony metal clusters have been determined by IR, UV-DRS, XPS and elemental analysis.The catalytic activities of these catalysts for the hydroformylation were studied. The experimental results show that supported metal clusters Ⅱ and Ⅲ give nearly the same activity as the homogeneous catalyst I . The conversion of 1-heptene and the yield of aldehydes are over 50% (catalyst used 0. 1 g; 1-heptene 1 ml. ). The product selectivity of aldehyde and alcohol is nearly 100% and no heptane is produced. Effect of the olefin structure can be seen by the rate order: l-Heptene>Diisobutene> Cyclohexene> 2-Octene>Styrene.

【基金】 国家自然科学基金资助课题
  • 【文献出处】 分子催化 ,Journal of Molecular Catalysis , 编辑部邮箱 ,1993年01期
  • 【被引频次】2
  • 【下载频次】50
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