几种铁的含氮双氧配合物的电子结构与催化氧化活性(Ⅱ)—赤道配体的作用

高等学校化学学报 ›› 1986, Vol. 7 ›› Issue (9): 821.

几种铁的含氮双氧配合物的电子结构与催化氧化活性(Ⅱ)—赤道配体的作用

宫宝安

烟台师范学院

收稿日期:1985-04-26 出版日期:1986-09-24 发布日期:1986-09-24

Electronic Structure and Catalytic Oxidation Activity on Some Fe Dioxygen Complexes Involving Nitrogen Element (Ⅱ)—The Efect of the Equatorrial Ligand

Gong Baoan

Department of Chemistry, Yantai Normal Institute, Yantai

Received:1985-04-26 Online:1986-09-24 Published:1986-09-24

摘要/Abstract

摘要： 本文用CNDO/2方法计算了一组铁的双氧配合物的电子结构。结果表明,处于赤道配体大环超共轭结构中,紧邻中心Fe离子的N原子、其介于C元素和O元素之间的电负性,维持了低价态Fe(Ⅱ)的稳定性,调整了Fe(Ⅱ)的d能级,从而利于Fe(Ⅱ)(d_xz和d(yz))→O₂(π_A)的电子迁移,阻止O₂(π_B)→Fe(Ⅱ)(d_z₂)的电子迁移。由此解释了金属酞菁化合物,催化烃类氧化活性与含氮配体间关联的实验结果。

Abstract: The electronic structures of a set of the Fe dioxygen complexes have been studied by using CNDO/2 computational method.The results showed that the apposite electronegativity of Nclement which is in aπ conjugated position ol the equatorial ligand and close by the central metal ion Fe(Ⅱ) between Cand Oelements has stabilized a low valence state and lias adjusted d orbital energies of the central metal Fe(Ⅱ),so that the electronic migration.Fe(Ⅱ) (d_xz,d_yz)→O₂(π_A) is forwarded and the electronic migration O₂(π_B)→Fe(Ⅱ) (d_z²) is prevcnted The experimental results arc satisfyingly explained on the basis of this computation.

TrendMD:

宫宝安. 几种铁的含氮双氧配合物的电子结构与催化氧化活性(Ⅱ)—赤道配体的作用. 高等学校化学学报, 1986, 7(9): 821.

Gong Baoan. Electronic Structure and Catalytic Oxidation Activity on Some Fe Dioxygen Complexes Involving Nitrogen Element (Ⅱ)—The Efect of the Equatorrial Ligand. Chem. J. Chinese Universities, 1986, 7(9): 821.