New Development of the Coordination Chemistry of Transition Metal-Oxygen Complexes

为了弄清氧转运和氧合反应相关的氧化催化剂和金属蛋白活性位点的功能和结构，系统地合成了可以通过适当的取代基修饰配位电子环境和空间环境的过渡金属-二氧配合物。主要发现如下1。高价双（μ-氧）化合物的化学性质镍和钴的双核μ-η2:η2-二氧配合物通过O-O裂解转化为高价双（μ-氧）化合物，这些化合物能够氧化碳氢化合物。这些化合物因其与甲烷单加氧酶活性组分的相关性而备受关注。含单核活性中心的金属蛋白的功能，如氧化芳烃的儿茶酚双加氧酶，已被成功地复制。第二行金属和早期过渡金属的双氧配合物的合成将合成研究的对象扩展到金属蛋白中不涉及的金属，揭示了金属蛋白中发现的第一行金属的特征。苯酚的区域选择性氧化聚合我们制备的二铜-二氧配合物对苯酚具有区域选择性氧化聚合生成聚对苯基氧化物的活性。生物无机研究的结果已应用于工业过程。其他方面，如与铜酶有关的单核铜氧配合物和芳烃在没有双氧的情况下的氧化也进行了研究。

In order to clarify functions and structure of the active sites of oxygenation catalysts and metalloproteins relevant to oxygen transport and oxygenation reactions, systematic synthetic study of transition metal-dioxygen complexes with hydrotrispyrazolylborates, which can easily modify the coordination electronic and steric environment by appropriate substituents, has been carried out. Key findings are as follows1. Chemistry of high valent bis(μ-oxo) speciesDinuclear μ-η2:η2-dioxygen complexes of nickel and cobalt are converted via O-O cleavage to high valent bis(μ-oxo) species, which are capable of oxygenation of hydrocarbons. The compounds attract much attention due to their relevance to the active species of methane monooxygenase.2. Oxygen activation on a mononuclear speciesThe function of metalloproteins containing mononuclear active center such as catechol dioxygenase, which oxidizes aromatics, has been successfully reproduced.3. Synthesis of dioxygen complexes of second row metals and early transition metalsThe target of the synthetic study has been extended to metals which are not involved in metalloproteins, and such study reveals the characteristic aspects of first row metal species found in the proteins.4. Regioselective oxidative polymerization of phenolsThe dicopper-dioxygen complexes prepared by us are found to be active for oxidative polymerization of phenols to give poly(p-phenylene oxide) in a regioselective manner. The result of a bioinorganic study has been applied to an industrial process.Other aspects such as mononuclear copper-oxygen complexes relevant to copper enzymes and oxidation of aromatics in the absence of dioxygen are also studied.