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

位阻配体体系新型金属催化剂的开发与应用

• 批准号: 13555257
• 负责人: FUJISAWA Kiyoshi
• 金额: $ 8.96万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13555257/
• 关键词: homogeneous catalysis; transition metal complex; dioxygen complex; polymerization of olefins; spectroscopic anal analysis; electronic structure; reaction mechanism; catalytic reaction

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

1.锰配合物对烯烃聚合反应具有催化反应性能。这种金属没有受到任何注意。为了更深入地了解反应机理，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根离子的吡唑根配合物。利用这些配合物，我们探索了一种不对称共轭加成反应3.通过铜（I）配合物与单质硫的反应，得到了μ，-η^2：η^2-二硫键配合物. 4.制备了非血红素铁加氧酶活性中心的模型化合物--α-酮铁（II）和羧酸铁（II）。α-酮酸羧酸配合物的反应速度比羧酸配合物快2个数量级，从而强调了α-酮酸官能团在α-酮酸依赖性铁酶激活氧中的关键作用5.利用新型空间位阻三（吡唑基）甲烷配体制备了铜（I）配合物.并比较了三吡唑硼酸氢盐体系和三吡唑甲烷体系的结构和性质

项目成果

K.Fujisawa, T.Ono, H.Aoki, Y.Ishikawa, Y.Miyashita, K.Okamoto, H.Nakazawa, H.Higashimura: "Copper(II) Complexes with a Novel Tris(3,5-diisopropyl-1-pyrazolyl)methane Ligand"Inorg.Chem.Commun.. 7. 330-332 (2004)

K.Fujisawa、T.Ono、H.Aoki、Y.Ishikawa、Y.Miyashita、K.Okamoto、H.Nakazawa、H.Higashimura：“具有新型 Tris(3,5-二异丙基-1) 的铜 (II) 配合物

Y.Miyashita, M.Sarnpda, Y.Yamada, K.Fujisawa, K.Okamoto: "Novel Alkoxo-Bridged Lanthanide(III) binuclear Complexes : Crystal Structure of Na_4[Yb_2(μ,-dpta-O)_2](N_4dpta-OH=1,3-Diamino-2hydroxypropane-N,N,N',N'-tetraacetic acid)"Chem.Lett.. 840-841 (2002)

Y.Miyashita、M.Sarnpda、Y.Yamada、K.Fujisawa、K.Okamoto：“新型烷氧基桥接镧系元素(III)双核配合物：Na_4[Yb_2(μ,-dpta-O)_2](N_4dpta)的晶体结构-OH=1,3-二氨基-2羟基丙烷-N,N,N,N-四乙酸)”Chem.Lett..840-841(2002)

Y.Miyashita, M.Sanada, Y.Yamada, K.Fujisawa, K.Okamoto: "Novel Alkoxo-Bridged Lanthanide(III) Dinuclear Complexes : Crystal Structure of Na_4[Yb_2(_-dpta-O)_2](N_4dpta-OH = 1,3-Diamino-2-hydroxypropane-N, N, N' N' -tetraacetic acid)"Chem.Lett. 840-841 (20

Y.Miyashita、M.Sanada、Y.Yamada、K.Fujisawa、K.Okamoto：“新型烷氧基桥接镧系元素 (III) 双核配合物：Na_4[Yb_2(_-dpta-O)_2](N_4dpta-) 的晶体结构

P.Chen, K.Fujisawa, M.E.Helton, K.D.Karlin, E.I.Solomon: "Spectroscopy and Bonding in Side-On and End-On Cu_2(S_2) Cores : Comparison to Peroxide Analogues"J.Am.Chem.Soc.. 125(印刷中). (2003)

P.Chen、K.Fujisawa、M.E.Helton、K.D.Karlin、E.I.Solomon：“侧面和端部 Cu_2(S_2) 核的光谱学和键合：与过氧化物类似物的比较”J.Am.Chem.Soc.. 125 （正在出版）。

D.Baba, H.Ishii, S.Higashiya, K.Fujisawa, T.Fuchigami: "Electroytic Partial Fluorination of Organic Compounds. 52.1 Regio- and Diastereoselective Anodic Fluorination of Thiazolidines"J.Org.Chem.. 66. 7020-7024 (2001)

D.Baba、H.Ishii、S.Higashiya、K.Fujisawa、T.Fuchigami：“有机化合物的电解部分氟化。52.1 噻唑烷的区域和非对映选择性阳极氟化”J.Org.Chem.. 66. 7020-7024