Download Catalytic Nitrene Transfer onto Isocyanide by a Redox

Catalytic Nitrene Transfer onto Isocyanide by a Redox-Active Ligand Zirconium Complex
Andy I. Nguyen
Mentor: Alan Heyduk
In an effort to bridge the gap between late- and early-metal reactivity, we have used redox-active ligands that
are capable of multielectron valence changes. These ligands on formally d0 metal centers have been shown to
facilitate “oxidative addition” of halogens and reductive coupling of C-C and N=N bonds. Recently, we have
used these ligands on tantalum(V) to generate imido complexes from organic azides(REF). This work reports
the reactivity of a zirconium(IV) complex with the previously reported [NNNcat]3- (bis(2-isopropylamino-4methoxyphenylamine)) redox-active ligand. Successive oxidation of [NNNcat]ZrCl(thf)2 by chlorine
establishes the availability of one- and two- electron oxidative states. The complex [NNNcat]ZrCl(CNtBu)2,
formed by ligand exchange of tetrahydrofuran with tert-butyl isocyanide, is able to catalyze the oxidative C=N
coupling of isocyanide and azide via a transient zirconium imido species.