Development of a Highly Efficient Complex Catalysts for Selective Aerobic Oxidation

在催化量的二氧（四聚乙烯基卟啉）钌络合物存在下，一氧化二氮（N_2O）以高收率和高选择性将三取代烯烃氧化成相应的环氧化物。采用N_2O催化氧化法对多种仲醇和苯醇制得相应的酮类和醛类，收率高。钌卟啉配合物催化氧化9,10 -二氢蒽衍生物时，在适当的反应条件下，苯碳的C-H氧化选择性地得到蒽醌，而在硫酸存在下选择性地得到氧化芳构化的蒽。研究了3-氧丁基氨基-钌配合物的制备。采用DFT研究了3-氧丁基氨基钴（II）配合物催化环丙化反应的总体反应途径和轴向配体的影响。用时间分辨傅里叶红外光谱法对钴（II）配合物与重氮乙酸酯的反应进行了跟踪。一般认为碳烯配合物中的金属-碳烯碳键应为双键，但理论和FT-IR分析表明钴-碳烯碳键为单键。期望这些观察结果能为氧化催化剂的设计提供一种有前途的方法。

In the presence of a catalytic amount of dioxo (tetramesitylporphyrinato) ruthenium (VI) complex, nitrous oxide (N_2O) oxidized trisubstituted olefins into the corresponding epoxides in good-to-high yields with high selectivity. Catalytic N_2O oxidation was successfully applied to various secondary and benzylic alcohols to afford the corresponding ketones and aldehydes in high yields. During the nitrous oxide oxidation of 9, 10-dihydroanthracene derivatives catalyzed by the ruthenium-porphyrin complexes, anthraquinones were selectively afforded by the C-H oxidation of the benzylic carbon under the appropriate reaction conditions, whereas anthracenes as a result of oxidative aromatization were selectively obtained in the presence of sulfuric acid. Preparation of 3-oxobutylideneaminato-rutheniumu complexes were also examined.A DFT study of the 3-oxobutylideneaminatocobalt (II) complex catalyzed cyclopropanation was performed to reveal the overall reaction pathway and the effects of the axial ligands. The reaction of cobalt (II) complexes with diazoacetate were traced by time-resolved FT-IR spectroscopy. It is generally considered that metal-carbene carbon bonds in carbene complexes should be double-bonded, however, the theoretical and FT-IR analyses revealed that the cobalt-carbene carbon bond was characterized as a single bond. It is expected that these observations would provide a promising method for design of oxidation catalysts.