锆（IV）氧化还原活性配体配合物与1,2-二苯基肼的催化反应活性
Catalytic reactivity of a zirconium(IV) redox-active ligand complex with 1,2-diphenylhydrazine.
作者信息
Blackmore Karen J, Lal Neetu, Ziller Joseph W, Heyduk Alan F
机构信息
Department of Chemistry, University of California, Irvine, California 92697, USA.
出版信息
J Am Chem Soc. 2008 Mar 5;130(9):2728-9. doi: 10.1021/ja710611v. Epub 2008 Feb 12.
Two-electron reactivity of [N2O2red]ZrL3 (1a, N2O2(red) = N,N'-bis(3,5-di-tert-butyl-2-phenoxy)-1,2-phenylenediamide, L = THF) was explored with halogens and 1,2-diphenylhydrazine. Despite a formal d0 zirconium(IV) metal center, halogen oxidative addition occurred to form [N2O2(ox)]ZrCl2(THF) (2) with two-electron oxidation of the ligand. This ligand redox activity allows catalytic reactivity with 1,2-diphenylhydrazine resulting in disproportionation to form aniline and azobenzene via a putative zirconium-imide intermediate.
利用卤素和1,2-二苯基肼对[N₂O₂red]ZrL₃（1a，N₂O₂(red)=N,N'-双(3,5-二叔丁基-2-苯氧基)-1,2-苯二酰胺，L =四氢呋喃）的双电子反应活性进行了研究。尽管是形式上的d⁰锆(IV)金属中心，但卤素发生氧化加成反应，形成了[N₂O₂(ox)]ZrCl₂(四氢呋喃)（2），同时配体发生双电子氧化。这种配体的氧化还原活性使得其与1,2-二苯基肼具有催化反应活性，通过假定的锆-亚胺中间体发生歧化反应生成苯胺和偶氮苯。
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