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Electron-deficient imines are shown to insert into the zirconium-carbon bond of azazirconacyclobutenes to generate new six-membered ring metallacycles. On heating, these expanded zirconacycles undergo a retro-[4 + 2] cycloaddition to generate alpha,beta-unsaturated imines in excellent yields and novel, fully characterized electron-deficient imidozirconocene complexes.

Reactions of Imines with Azazirconacyclobutenes and Generation of Electron-Deficient Imidozirconocene Complexes