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Dinickel-Catalyzed N═N Bond Rotation
Christopher J Rybak1, John M Andjaba1, Chengyi Fan1
1Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907, United States.
Abstract:
Azoarenes function as molecular switches that can be triggered by external stimuli, such as heat, light, and electrochemical potential. Here, we show that a dinickel catalyst can induce cis/trans isomerization in azoarenes through a N═N bond rotation mechanism. Catalytic intermediates containing azoarenes bound in both the cis and trans forms are characterized. Solid-state structures reveal the importance of π-back-bonding interactions from the dinickel active site in lowering the N═N bond order and accelerating bond rotation. The scope of the catalytic isomerization includes high-performance acyclic, cyclic, and polymeric azoarene switches.
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