SCHEDULED MAINTENANCE
Octahedral cobalt(III) complexes of the chloropentammine type. Part IX. The acid hydrolysis of cis-chlorohydroxylaminebis(ethylenediamine)cobalt(III) nitrate
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.
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