Title: Substitution reactions at octahedral complexes:
1Substitution reactions at octahedral
complexes acid and base hydrolysis
2Acid hydrolysis
- Protonation of a ligand which then dissociates
from the metal
See Questions 1-3
3Acid hydrolysis
- Protonation of an inert ligand labilises other
ligands
4(No Transcript)
5Acid hydrolysis
- Protonation of the metal itself leads to
labilisation of a ligand
6Base hydrolysis at a transition metal complex is
based on the observation that reactions of the
type are accelerated by increasing OH-
ML4(LH)(X)n OH- ? ML4(LH)(OH)n X-
and the saturation behaviour seen with
acid-catalysed reactions (Chapter 2) does not
occur
Mechanism proposed by Garrick and called the DCB
Mechanism
7(1)
Now
8But
9Substituting into (1)
10Base hydrolysis is usually considerably faster
than acid hydrolysis because of stabilisation of
the transition state by the conjugate base.
Hence a ? donor ligand such as OH- or NH2- is
required for this mechanism