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1、学生吴若秋指导老师鲁统学生吴若秋指导老师鲁统部教授部教授 研究意义 碳-碳键的活化与断裂在石油化工、材料工业、有机合成等领域具有重要的研究意义和应用价值。目前此类反应大多数需要在长时间加热甚至加压的条件下进行，并且伴随有副反应和环境污染。研究在较温和的条件下对碳-碳键活化，将是具有挑战性的课题。 实验结果与讨论一一. ESI-MS. ESI-MS T: 12001400160018002000m/z1770.601714.931092.131260.671888.401501.33 2004006008001000 10 20 30 40 50 60 70 80 90 100834.93268
2、.00368.00635.07Cu2L1(ClO4)3+Cu2L1(ClO4)+Cu2L1(ClO4)22+Cu2L12+ 0 T:120014001600180020001845.001475.471760.671210.071887.602004006008001000m/z 0102030405060708090 100471.40562.27634.93CuL1 +Cu2L1(-CN)+Cu2L1(ClO4)+268.00Cu2L12+CuCu2 2L L1 1(ClO(ClO4 4) )4 4溶于溶于CHCH3 3CNCN8080加热加热5 5天（绿色）天（绿色） CuCu2 2L
3、L1 1(ClO(ClO4 4) )4 4溶于溶于CHCH3 3CNCN立即测立即测 ( (蓝紫色）蓝紫色） 实验结果与讨论 T:200400600800100012001400160018002000m/z 0102030405060708090 100 564.33386.131239.131879.131325.871475.871636.071904.00Cu2L1(-CN)+Cu2L1(H2O)2(ClO4)22+CuCu2 2L L1 1(ClO(ClO4 4) )4 4溶于溶于CHCH3 3CNCN8080加热加热8 8天（黄色）天（黄色）一、一、ESI-MSESI-MS（续）（
4、续）SimulationCu2C25H38N7ProfileResolution:Daltons 0.25at 5% heightCharges 1Chrg dist 0Ions 912Min Ion Ab. 1e-020Min Ions 5000Max Ions. 20000562564566568570572574576578580m/z0.000.050.100.150.200.250.300.35562.18564.17563.18565.18566.17567.17574.19575.20577.20578.21 T:560561562563564565566567568569570
5、m/z 0102030405060708090 100564.17562.18563.21565.20566.17 567.15ZoomscanCu2L1(-CN)+理论图 实验结果与讨论二二. . 紫外可见光谱紫外可见光谱CuCu2 2L L1 1(ClO(ClO4 4) )4 4溶于溶于DMFDMF( (蓝紫色）蓝紫色）CuCu2 2L L1 1(ClO(ClO4 4) )4 4溶于溶于CHCH3 3CNCN即测即测（蓝紫色）（蓝紫色） 实验结果与讨论二二. . 紫外可见光谱（续）紫外可见光谱（续）CuCu2 2L L1 1(ClO(ClO4 4) )4 4溶于溶于CHCH3 3CNCN
6、80 80加热加热5 5天天 ( (绿色绿色) )CuCu2 2L L1 1(ClO(ClO4 4) )4 4溶于溶于CHCH3 3CNCN 80 80加热加热8 8天天 ( (黄色黄色) )色谱纯乙腈溶剂(蓝紫色)配合物乙腈溶液80加热20天(蓝绿色)加水的配合物乙腈溶液80加热20天(黄绿色)三三. .气相色谱法测定催化活化反应产物气相色谱法测定催化活化反应产物( (甲醇甲醇) )含量含量 实验结果与讨论四四. .配合物配合物 CuCu2 2L L1 1(ClO(ClO4 4) )4 4对对C C6 6H H5 5CNCN的催化活化的催化活化 配合物配合物CuCu2 2L L1 1(ClO
7、(ClO4 4) )4 4苯甲腈溶液在苯甲腈溶液在 结论结论 大环双核铜配合物大环双核铜配合物 CuCu2 2L L1 1(ClO(ClO4 4) )4 4、 Cu Cu2 2L L2 2(ClO(ClO4 4) )4 4对对CHCH3 3CNCN、C C6 6H H5 5CNCN等腈化物的碳等腈化物的碳- -碳键有催化活化作碳键有催化活化作用。用。 配合物在配合物在CHCH3 3CNCN中加热，生成氰根桥联产物与甲中加热，生成氰根桥联产物与甲醇，并且醇，并且H H2 2O O也参与了反应；在催化活化过程中，双核也参与了反应；在催化活化过程中，双核铜的配位构型发生改变。示意如下：铜的配位构型发
8、生改变。示意如下： 今后的工作与展望今后的工作与展望 测定在一定条件下的催化活化反应速率，从而计算出其活性；研究大环双核铜对其它腈化物的催化效果；继续研究其它大环双核金属配合物的催化活化性能。 参考文献参考文献: :： 1 Zhu Hai-Liang, Zheng Li-Min, Fu De-Gang, et al. The Synthesis, Structure and 1 Zhu Hai-Liang, Zheng Li-Min, Fu De-Gang, et al. The Synthesis, Structure and SOD-like Behaviors of a -imidazo
9、latodicopper() Complex with a Binucleating SOD-like Behaviors of a -imidazolatodicopper() Complex with a Binucleating Hexaazamacrocycle. Hexaazamacrocycle. J. of Inorg. Biochem,J. of Inorg. Biochem, 19981998, 70: 211-213., 70: 211-213. 2 Lu,Tongbu, Zhuang Xiaomei, Li Yanwu, et al. C-C Bond Cleavage
10、of 2 Lu,Tongbu, Zhuang Xiaomei, Li Yanwu, et al. C-C Bond Cleavage of Acetonitrile by a Dinuclear Copper(II) Cryptate.Acetonitrile by a Dinuclear Copper(II) Cryptate. J. Am. Chem. Soc.,J. Am. Chem. Soc., 20042004, 126(16): , 126(16): 4760-4761.4760-4761. 3 Jean-louis Pierre, Pierre Chautemps, Sidi R
11、efaif, et al. Imidazolate-bridged 3 Jean-louis Pierre, Pierre Chautemps, Sidi Refaif, et al. Imidazolate-bridged Dicopper(II) and Copper-Zinc Complexes of a Macrobicyclic Ligand(Cryptand). A Dicopper(II) and Copper-Zinc Complexes of a Macrobicyclic Ligand(Cryptand). A Possible Modle for the Chemistr
12、y of Cu-Zn Superoxide Dismutase. Possible Modle for the Chemistry of Cu-Zn Superoxide Dismutase. J. Am. Chem. J. Am. Chem. Soc.Soc., , 19951995, 117: 1965-1937., 117: 1965-1937. 4 Rached Menif, Joseph Reibenspies, Rthur, A E, Martell.4 Rached Menif, Joseph Reibenspies, Rthur, A E, Martell. Inorg. Ch
13、em., Inorg. Chem., 19911991, , 30: 3446.30: 3446. 5 Benedikt Ahlers, Karl Cammann, Sabine Warzeska, Roland Kramer. Molecular 5 Benedikt Ahlers, Karl Cammann, Sabine Warzeska, Roland Kramer. Molecular Recognition of Cynaide by a Dicopper(Recognition of Cynaide by a Dicopper() Macrocyclic Ionophore Co
14、nstruction of ) Macrocyclic Ionophore Construction of a Cyanide-Selective Liquid-Membrane Electrode. a Cyanide-Selective Liquid-Membrane Electrode. Angew. ChemAngew. Chem. . Int. Ed. EnglInt. Ed. Engl, , 19961996, 35(18): 2141-2143., 35(18): 2141-2143. 6 Valeria Amendola, Emanuela Bastianello, Luigi
15、 Fabbrizzi, Catlo Mangano, et al. 6 Valeria Amendola, Emanuela Bastianello, Luigi Fabbrizzi, Catlo Mangano, et al. Halide-Ion Encapsulation by a Flexible Dicopper (Halide-Ion Encapsulation by a Flexible Dicopper () Bis-Tren Cryptate. ) Bis-Tren Cryptate. Angew. Angew. ChemChem. . Int. Ed. EnglInt. E
16、d. Engl, , 20002000, 39(16): 2917-2920., 39(16): 2917-2920. 7 Robert W. Hay, Thomas Clifford, David T. Richens, Philip Lightfoot. Binuclear 7 Robert W. Hay, Thomas Clifford, David T. Richens, Philip Lightfoot. Binuclear copper(), nickel(), cobalt() and zunc() complex of the macrocyclic 1, 4, 7, copp
17、er(), nickel(), cobalt() and zunc() complex of the macrocyclic 1, 4, 7, 16, 19 22 hexaaza9.9 metacyclophane(L). Crystal structure of 16, 19 22 hexaaza9.9 metacyclophane(L). Crystal structure of CuCu2 2LClLCl4 4 0.50.5CuCu2 2LClLCl3 3ClOClO4 4dmf and the copper complex catalysed hydrolysis of dmf and
18、 the copper complex catalysed hydrolysis of the phosphotriester 2,4 dinitrophenyldiethylphosphate. the phosphotriester 2,4 dinitrophenyldiethylphosphate. polyhedron, polyhedron, 20002000, 17: , 17: 1485 1492.1485 1492. 致谢 非常感谢鲁老师的谆谆教导与无微不至的关非常感谢鲁老师的谆谆教导与无微不至的关怀，给我提供了许多宝贵的知识和经验，更重要的怀，给我提供了许多宝贵的知识和经验，更重要的是教会我如何去学习化学、做实验和搞科研的方是教会我如何去学习化学、做实验和搞科研的方法，这些都必将使我受益终身。法，这些都必将使我受益终身。 感谢创新基金给我这次机会，让我在浩瀚无边感谢创新基金给我这次机会，让我在浩瀚无边的化学世界中遨游，领略其中奥妙。的化学世界中遨游，领略其中奥妙。 另外还要感谢鲁老师实验组的每一位成员，特另外还要感谢鲁老师实验组的每一位成员，特别是庄师姐的细心指导。感谢每一位帮助和支持我别是庄师姐的细心指导。感谢每一位帮助和支持我的老师和同学们，谢谢！的老师和同学们，谢谢！ 谢谢大家！
