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Kinetics and Mechanism of the Demetallation of Macrocyclic Nickel(II) Complexes by Cyanide by Liselotte Siegfried; Thomas A. Kaden is a Chemistry article available to read on EtoBox.

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## Abstract The kinetics and the mechanism of the cyanide‐induced demetallation of a series of Ni^2+^ complexes with macrocyclic ligands of different ring size (12‐ to 14‐membered; see **1**–**4**) and steric constraints was studied. Although the rates differ by almost five orders of magnitude when compared to each other under fixed experimental conditions (pH 10.5, [CN^−^]=10^−2^ M), all reactions proceed through the relatively rapid formation of cyano adducts [Ni(CN)~__n__~L] (__n__=1, 2), which then react with additional CN^−^ or HCN to give the final products. Of paramount importance for the reaction rate is the geometry and configuration of the cyano adducts [Ni(CN)~__n__~L] (__n__=1,2). __cis__‐Dicyano derivatives with a folded macrocycle react faster than __trans__‐compounds. In the case of (1,4,8,11‐tetraazacyclotetradecane)nickel(2+) ([Ni (**4**)]^2+^), which gives a __trans‐__ dicyano adduct, the base‐catalyzed N‐inversion necessary to obtain the __cis‐__dicyano derivative becomes rate determining at high CN^−^ concentrations.

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Author

Liselotte Siegfried; Thomas A. Kaden

Publisher

John Wiley and Sons; Wiley (John Wiley & Sons); Wiley-Blackwell; Wiley (ISSN 0018-019X)

Published

2005

Language

EN

Field

Chemistry (Physical Sciences)