Issue 1, 2005
From the journal:

Dalton Transactions

Selective metal promoted hydrolysis of nitrile groups in the side chain of tetraazamacrocyclic Cu2+-complexes

Liselotte Siegfried,a   Antonio Comparone,a   Markus Neuburgera  and  Thomas A. Kaden*a  

* Corresponding authors

a Department of Chemistry, Spitalstr. 51, Basel, Switzerland
E-mail: Th.Kaden@unibas.ch

Abstract

The metal promoted hydrolysis of nitrile groups in the side chains of tetraazamacrocyclic Cu2+ complexes has been studied by stopped-flow techniques. It is shown that the reaction proceeds by an intramolecular attack of an axially coordinated OH− onto the nitrile group to give the corresponding amide. In alkaline solution the amide then deprotonates and binds to the axial position of the Cu2+ thus preventing further coordination of an OH−. This explains mechanistically that in the Cu2+ complexes of macrocycles carrying two nitrile functions only one is selectively hydrolysed. The nitrile hydrolysis has also been used on a preparative scale to synthesize tetraazamacrocycles with two different side chains. X-Ray diffractions of several products are presented to confirm the structures and the results from the kinetics and equilibria measurements.

Graphical abstract: Selective metal promoted hydrolysis of nitrile groups in the side chain of tetraazamacrocyclic Cu2+-complexes

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Article information

DOI
https://doi.org/10.1039/B412857P
Article type
Paper
Submitted
19 Aug 2004
Accepted
28 Oct 2004
First published
18 Nov 2004

Dalton Trans., 2005, 30-36

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Selective metal promoted hydrolysis of nitrile groups in the side chain of tetraazamacrocyclic Cu2+-complexes

L. Siegfried, A. Comparone, M. Neuburger and T. A. Kaden, Dalton Trans., 2005, 30 DOI: 10.1039/B412857P

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