Development of effecient and stereoselective Non-heme type catalyst by introduction of stereocontrol

立体选择性氧化是一种重要的化学过程，需要高效、高立体选择性的铁络合物作为环境友好的工艺。由于我们开发的铁(III)配合物的双核结构是烷基单加氧酶等非血红素双核铁酶的关键核心结构，因此研究了通过在配体中引入手性取代基和I或空间位阻取代基来提高合成的双核铁(III)配合物的催化氧化性能。合成了几种N_2O_2手性四齿配体，包括乙二胺外部的酰胺结合部位及其双核铁(III)配合物。考察了该催化剂对过氧化氢亚磺化反应的催化性能。与含仲酰胺或非手性配体的络合物相比，含叔胺的手性配体的铁(III)络合物的活性最高。为了研究这些配合物的结构细节，我们对这些手性配体的单核金属配合物进行了研究，结果表明，含仲胺的手性配体与含叔胺的手性配体的IF金属配合物的结构是相反的。络合物的螺旋性也受到反阴离子的影响。

Stereoselective oxidation is an important chemical process in academy and / or industry and iron complexes with high efficiency and high stereoselectivity are required for environmentally friendly process. Since a dinuclear core structure of iron(III) complex developed by us is a key core structure of nonheme dinuclear iron enzyme such as alkane monooxygenase, it has been studied enhancing the catalytic oxidation properties of the synthesized dinuclear iron(III) complexes by means of introduction of chiral substitute and I or sterically hindered substitutes in the ligands. Several N2O2 chiral tetradentate ligand including amide binding sites external to the ethylenediamine and their dinuclear iron(III) complexes have been synthesized. The catalytic properties for sulfoxidation with hydrogen peroxidewere examined. The iron(III) complex with chiral ligand including tertiary amides is most active compared to the complexes including secondary amide nor achiral ligands. To study the structural detail of these complexes, mononuclear metal complexes with these chiral ligands have been examined and it was clear that the structure of metal complex with chiral ligand including secondary amine is opposite to that if metal complex with chiral ligand including tertiary amides. The helicity of the complex is also influenced by counter anions.