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Catalytic Reactivity of a Zirconium(IV) Redox-Active Ligand Complex with 1,2-Diphenylhydrazine

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journal contribution
posted on 05.03.2008, 00:00 by Karen J. Blackmore, Neetu Lal, Joseph W. Ziller, Alan F. Heyduk
Two-electron reactivity of [N2O2red]ZrL3 (1a, N2O2red = 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 [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.