MECHANISM OF THE BASE HYDROLYSIS OF ESTERS
The hydroxide nucleophiles attacks at the electrophilic
, breaking the bond and creating the
The intermediate collapses, reforming the
results in the loss of the leaving group the alkoxide,
, leadingto the carboxylic acid.
An acid / base reaction. A very rapid equilibrium where thealkoxide,
functions as a base deprotonating the carboxylicacid,
, (an acidic work up would allow the carboxylicacid to be obtained from the reaction).
Base Hydrolysis of Bis(acetylacetonato)nitridotechnetium(V)1, 2:
Base hydrolysis of bis(acetylacetonato)nitridotechnetium(V), [TcN(acac) 2], was investigated inan aqueous3acetonitrile solution. The reaction kinetics was monitored by UV-visible spectroscopy. The basehydrolysis involves substitution of water molecules for coordinated acetylacetone (this stage isindependentof the concentration of hydroxide ion), followed by slow decomposition of the intermediate complex byan attack of the hydroxide ion. The respective rate constants were determined at 25oC.
Base-Catalysed Hydrolysis: The CB Mechanism
As mentioned earlier the rates of substitution of octahedral complexes are not sensitive tothe nature of the entering group-with one exception. In basic media Co(III) complexes havingligands of the type NH
NH are sensitive to the nature of the entering group.The base catalysed reactions are generally much more rapid than anation or hydrolyses in acidsolution. The agreed mechanism, involves the removal of a proton from the amine ligand. Thisstep is generally very fast, (10
faster), and represents rapid pre-equilibrium to the ratedetermining loss of leaving group.