合成了四种金属铜(Ⅱ)-四氮配合物,并用初始速率法研究了25 ℃时四种配合物催化H2O2氧化偶合2,6-二甲基苯酚生成3,3′,5,5′-四甲基联苯二醌反应的动力学. 结果表明此偶合反应符合Michaelis-Menten酶催化动力学,并由此获得了反应在不同配合物和不同pH值情况下的动力学参数k2和Km. 研究还发现不同的铜配合物其催化活性有不同的最适pH,具有较好电子共轭效应和合适刚柔性结构的铜配合物更有利于反应的进行. 对此催化反应的动力学机理研究发现,铜配合物的一级酸式电离中间物种是反应的主要催化活性物种. 质谱分析表明,此类铜配合物都能催化2,6-二甲基苯酚进行C - O偶合反应生成不同聚合度的高分子.
参考文献
| [1] | Sarkanen K V;Ludwig C H.Lignins[M].New York: Wiley-Interscience,1971 |
| [2] | Mason H S .[J].Journal of Biological Chemistry,1948,172:83. |
| [3] | Davin L B;Wang H B;Crowell A L;Bedgar D L, Martin D M, Sarkanen S, Lewis N G .[J].Science,1997,275(5298):362. |
| [4] | Jiang F;Jiang B;Yu X;Zeng X .[J].Langmuir,2002(18):6769. |
| [5] | Cheng SQ.;Meng XG.;Yu XQ.;Zeng XC. .Metallomicellar catalysis hydrolysis of p-nitrophenyl picolinate catalyzed by copper(II), nickel(II),and zinc(II) complexes of long alkyl pyridine ligands in micellar solution[J].Journal of Colloid and Interface Science,2000(2):333-337. |
| [6] | 李慎新,李建章,谢家庆,陈勇,孟祥光,胡常伟,曾宪诚.Schiff碱铜配合物模拟过氧化物酶的研究[J].化学学报,2004(06):567-572. |
| [7] | Hay A S;Blanchard H S;Endres G F;Eustance J W .[J].Journal of the American Chemical Society,1959,81(23):6335. |
| [8] | Hay AS. .Polymerization by oxidative coupling: Discovery and commercialization of PPO (R) and Noryl (R) resins [Review][J].Journal of Polymer Science, Part A. Polymer Chemistry,1998(4):505-517. |
| [9] | Mijs W J;van Dijk J H;Huysmans W G B;Westra J G .[J].Tetrahedron,1969,25(08):4233. |
| [10] | Walling C;Hodgdon Jr R B .[J].Journal of the American Chemical Society,1958,80(01):228. |
| [11] | Price C C;Nakaoka K .[J].Macromolecules,1971,4(04):363. |
| [12] | Talsi E P;Shaikhutdinova N I;Shubin A A;Chinakov V D, Khlebnikov B M, Yudkin B I, Nekipelov V M, Zamaraev K I .[J].Journal of Molecular Catalysis(China),1990,57(03):325. |
| [13] | Baesjou P J;Driessen W L;Challa G;Reedijk J .[J].Journal of the American Chemical Society,1997,119(51):12590. |
| [14] | Viersen F J;Challa G;Reedijk J .[J].Polymer,1990,31:1368. |
| [15] | Camus A;Garozzo M S;Marsich N;Mari M .[J].Journal of Molecular Catalysis A:Chemical,1996,112(03):353. |
| [16] | Ikeda R;Sugihara J;Uyama H;Kobayashi S .[J].Macromolecules,1996,29(27):8702. |
| [17] | Baesjou P J;Driessen W L;Challa G;Reedijk J .[J].Journal of Molecular Catalysis A:Chemical,1996,110(03):195. |
| [18] | Baesjou PJ.;Challa G.;Reedijk J.;Driessen WL. .A kinetic study of the copper-catalysed oxidative coupling of 2,6-dimethylphenol. The role of copper, base and phenol concentrations[J].Journal of molecular catalysis, A. Chemical,1998(3):273-283. |
| [19] | Schrauzer G N;Sibert J W;Windgassen R J .[J].Journal of the American Chemical Society,1968,90(24):6681. |
| [20] | Menger F M;Portnoy C E .[J].Journal of the American Chemical Society,1967,89(18):4698. |
| [21] | Merrell P H;Urbach F L;Arnold M .[J].Journal of Chemical Education,1977,54(09):580. |
| [22] | Kirschner S.Inorganic Syntheses, Vol 23[M].New York:John Wiley & Sons,1985:82. |
| [23] | Nishino H;Satoh H;Yamashita M;Kurosawa K.[J].Journal of the Chemical Society Perkin Transactions 2,1999(09):1919. |
| [24] | Tagaki W;Ogino K;Tanaka O .[J].Bulletin of the Chemical Society of Japan,1991,64(01):74. |
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