Mechanism and steric course of octahedral aquation. Part X. The preparation, properties, aquation, and anation of some cis-bisunidentato-(1,4,8,11-tetra-azacyclotetradecane)cobalt(III) cations
- 1 January 1968
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc. A
- p. 1549-1555
- https://doi.org/10.1039/j19680001549
Abstract
The preparation and characterisation of a series of complexes of the type, cis-[Co cyclam X2]Y (X =½CO3, Cl, Y = Cl; X = NO2, N3, NCS, Y = NO3 and ½[PtCl6]; cyclam = 1,4,8,11-tetra-azacyclotetradecane) and cis- and trans-[Co cyclam(H2O)2](ClO4)3 are reported. In all the preparative experiments, substitution takes place with complete retention of configuration although a slow subsequent isomerisation to the more stable trans isomer can be observed. The kinetics of the aquation of the cis-dichloro-cation have been studied over a range of temperature. This complex is some 15,000 times more labile than its trans isomer at 25°, the effect arising from a much lower activation energy. The anation of cis-[Co cyclam Cl H2O]2+ by thiocyanate has also been investigated. The reactions of the cis isomer are compared with those of the trans isomers and also with those of the corresponding bis(ethylenediamine)complexes.Keywords
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