Document Type

Article

Publication Date

2009

Abstract

The spontaneous oxidation of an amine group to an imine has been observed experimentally in an octa-aza macrocyclic dinucleating ligand LH4 coordinated to CuII. The reaction is bimolecular and spontaneous in which amine groups of one macrocycle are oxidised and the CuII centres of a second macrocyclic complex are reduced. No additional oxidating or external base agents are required. DFT calculations are carried out to compare the reaction with that recently reported for a ligand coordinated to an FeIII centre, but which requires an external base as proton acceptor. The computational results show that the copper and iron catalysed amine to imine reactions proceed via different mechanisms.

Comments

This article was originally published as:

Christian, G. J., Arbuse, A., Fontrodona, X., Martinez, M. A., Llobet, A., & Maseras, F. (2009). Oxidative dehydrogenation of an amine group of a macrocyclic ligand in the coordination sphere of a CuII complex. Dalton Transactions, (30), 6013–6020. doi:10.1039/B902947H

Dalton Transactions is published by RSC Publishing and may be accessed here

At the time of writing Dr. Gemma Christian was at the Institute of Chemical Research of Catalonia.

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