Octahedral cobalt(III) complexes of the chloropentammine type. Part IX. The acid hydrolysis of cis-chlorohydroxylaminebis(ethylenediamine)cobalt(III) nitrate
- 1 January 1967
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc. A
- p. 573-575
- https://doi.org/10.1039/j19670000573
Abstract
The hydrolysis of cis-chlorohydroxylaminebis(ethylenediamine)cobalt(III) nitrate in acidic solution has been studied over a range of both acid concentrations and temperatures. At low acid concentrations, the reaction is complicated by a spontaneous redox process, and the observed first-order rate constants decrease as the amount of acid in solution increases until a limiting condition is reached (>0·4N acid); product analysis by spectrophotometry at this stage indicates that the reaction involved is almost entirely solvolytic aquation. The higher reaction rate and lower activation energy compared with the cis-chloroammine complex suggest specific hydrogen bonding of the hydroxylamine ligand which brings a water molecule into a position highly favourable for nucleophilic attack. This is assisted by the inductive effects of the hydroxyl substituent in the hydroxylamine ligand.Keywords
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