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Substitution reactions at octahedral complexes:

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Substitution reactions at octahedral complexes: acid and base hydrolysis Chapter 5 Acid hydrolysis Protonation of a ligand which then dissociates from the metal See ... – PowerPoint PPT presentation

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Title: Substitution reactions at octahedral complexes:


1
Substitution reactions at octahedral
complexes acid and base hydrolysis
2
Acid hydrolysis
  • Protonation of a ligand which then dissociates
    from the metal

See Questions 1-3
3
Acid hydrolysis
  • Protonation of an inert ligand labilises other
    ligands

4
(No Transcript)
5
Acid hydrolysis
  • Protonation of the metal itself leads to
    labilisation of a ligand

6
Base 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
8
But
9
Substituting into (1)
10
Base 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
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