Development and Application of Novel Metal Catalysts with Steritically Hindered Ligand Systems

1.锰配合物对烯烃聚合反应具有催化作用。这种金属没有受到任何关注。为了更好地了解反应机理，我们正在合成锰(II)-烷基配合物2.我们表征了具有空间位阻的吡唑啉配合物。利用这些配合物，我们探索了一种不对称的共轭加成反应3.铜(I)配合物与单质硫反应得到了μ，-η^2：η^2-二硫配合物.制备了单核铁(II)、α-酮和羧酸类化合物作为非血红素铁加氧酶活性中心的模型。α-酮酸羧酸盐配合物的反应速度比羧酸盐配合物快2个数量级，从而强调了α-酮官能团在α-酮酸依赖的铁酶的氧活化中所起的关键作用。我们还比较了三(吡唑基)硼酸盐体系和三(吡唑基)甲烷体系的结构和性质

1.Manganese complexes have the catalytic reaction properties for olefin polymerization reactions. This metal has not been paid any attentions. In order to get more insight on the reaction mechanism, we are now synthesizing manganese(II)-alkyl complexes2.We characterized the pyrazolato complexes with steritically hindered pyrazolate ions. By use of these complexes, we explored an asymmetric conjugate addition reaction3.The μ,-η^2 : η^2-disulfido complex was obtained by the reaction of the copper(I) complex with elemental sulfur. Its detailed electronic structure was examined4.Mononuclear iron(II) α-keto and carboxylate compounds were prepared as models for the active sites of nonheme iron oxygenases. The α-keto acid carboxylate complexes react 2 orders of magnitude faster than the carboxylate complexes, thus emphasizing the key role that the α-keto functionality plays in oxygen activation by α-keto acid-dependent iron enzymes5.The copper(I) complexes were prepared by using the novel stertically hindered tirs(pyrazolyl)methane ligands. We also compared the structures and properties between hydrotris(pyrazolyl)borate systems and tris(pyrazolyl)methane systems