Catalytic reactivity of a zirconium(IV) redox-active ligand complex with 1,2-diphenylhydrazine
Catalytic reactivity of a zirconium(IV) redox-active ligand complex with 1,2-diphenylhydrazine
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DOI：
10.1021/ja710611v
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发表时间：
2008-03-05
影响因子：
15
通讯作者：
Heyduk, Alan F.
中科院分区：
文献类型：
--
作者：
Blackmore, Karen J.;Lal, Neetu;Heyduk, Alan F.
[N2O2red]ZrL3（1a，N2O2red = N,N-双（3,5-二叔丁基-2苯氧基）-1,2-苯二酰胺，L = THF）与卤素和 1,2-二苯肼的双电子反应性进行了研究。尽管存在正式的 do 锆（M 金属中心），但配体的双电子氧化仍发生卤素氧化加成，形成 [N2O2ox]ZrCl2(THF)(2)。这种配体氧化还原活性允许与 1,2-二苯肼发生催化反应，从而通过推定的锆酰亚胺中间体歧化形成苯胺和偶氮苯。
Two-electron reactivity of [N2O2red]ZrL3 (1a, N2O2red = N,N-bis(3,5-di-tert-butyl-2phenoxy)-1,2-phenylenediamide, L = THF) was explored with halogens and 1,2-diphenylhyrazine. Despite a formal do zirconium(M metal center, halogen oxidative addition occurred to form [N2O2ox]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.