Elucidation of the relationship between the structure and the reactivity of transition metal dioxygen complexes

为了了解中心金属与双氧配合物的结构和反应性之间的关系，对含三吡唑硼酸氢酯的双氧配合物进行了系统的合成研究。因此，各种各样的双氧配合物已被制备和光谱和晶体学方法，其特征在于，所获得的结果的基础上，提出了一种有效的活化方法过氧物种1。介绍了一种制备双氧配合物的新方法，即：e.羟基金属络合物和过氧化氢之间的脱水缩合反应已经被开发，并且已经发现了多种双氧加合物2。制备了钴和镍的双金属-μ-氧代物种，并通过X射线晶体学对其进行了充分表征。这些物种能够取代配体的烃基部分，结合相关工作，我们的结果现在被认为是这种物种的存在和高活性的证据，这被认为是参与甲烷单加氧酶的活性中心3。氧加合物的结构取决于中心金属的d-轨道能级和中心金属与过氧化物配体之间的几何排列4。过氧中间体的O-O均分解产生金属氧自由基，是将非活性过氧物质转化为活性氧化剂的一种有前途的方法，并且发现O-O均分解取决于中心金属d轨道的能级4。第二行金属络合物含有活性氧物种，如M-OOH物种，这一直被认为是非常不稳定的，充分表征和氧活化过程中理解在分子水平上

For the understanding of the relationship between the central metal and the structure and reactivity of the dioxygen complexes a systematic synthetic study of dioxygen complexes bearing the hydrotrispyraxolylborate has been carried out. As a result, a variety of dioxygen complexes have been prepared and characterized by spectroscopic and crystallographic methods and, on the basis of the results obtained, an effective activation method for peroxo species is proposed1. The new preparative method for dioxygen complexes, i. e. dehydrative condensation between hydroxometal complex and hydrogen peroxide, has been developed and a variety of dioxygen adducts have been prepared2. The dimetalbis-μ-oxo species of cobalt and nickel were prepared and fully characterized by X-ray crystallography. The species are able to oxygenate the hydrocarbyl moieties of the ligand and combined with the related works our result is now regarded as evidence for thee occurrence and high activity of such a species, which is proposed to be involved in the active site of methane monooxygenase3. The structure of the oxygen adducts are dependent on the d-orbital energy level of the central metal and the geometrical arrangement between the central metal and the peroxide ligand4. O-O homolysis of a peroxo intermediate leading to metaloxy radical resulting is a promising method for conversion of the inactive peroxo species into an active oxygenating reagent and the O-O homolysis is found to be dependent on the energy level of d-orbitals of the central metals4. Second row metal compelxes containing an active oxygen species such as M-OOH species, which have been believed to be very unstable, are fully characterized and oxygen-activation processes are understood at a molecular level