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Thermodynamic and kinetic stability
of metal complexes, Part 2, Kinetic
stability
Kinetic
stability
Labile
complexes
Inert
complexes
Reaction through dissociative mechanism
Outer orbital complexes
sp3d2 hybridization, larger and weaker M-L bonds (higher
energy)
Inner orbital complexes
d2sp3 hybridization, shorter and stronger M-L bonds (lower
energy)
Inner orbital complexes: Inert always
Outer orbital complexes: Labile always
Reaction through associative mechanism
Outer orbital and inner orbital complexes with low lying
unhybridized metal d-orbitals.
These orbitals are center attack by the incoming ligand in
associated mechanism of substitution.
Inert complexes
Electrons are present in the unhybridized d-orbitals.
Labile complexes
Vacant unhybridized d-orbitals.
[MnCl6]3- = Labile
[Cr(CN)6]3- = Inert
d2sp3
XX XX XX XX XX XX
XX XX XX XX XX XX
sp3d2
Inner orbital complexes
6 4
)
6 3
in eg
Dissociative mechanism: Square pyramidal intermediate
Loss in CFSE = CFSE of SP – CFSE of Oh
Associate mechanism: Pentagonal bipyramidal transition state
Loss in CFSE = CFSE of PBP – CFSE of Oh
If the loss in CFSE negative = inert complex
If the loss in CFSE positive or zero = labile complex
Basolo and Pearson calculated CFSE for LS and HS square
pyramidal and pentagonal bipyramidal complexes.
Thermodynamic and kinetic stability, Part 2, kinetic stability.pptx

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Thermodynamic and kinetic stability, Part 2, kinetic stability.pptx

  • 1. Thermodynamic and kinetic stability of metal complexes, Part 2, Kinetic stability
  • 3.
  • 4.
  • 5. Reaction through dissociative mechanism Outer orbital complexes sp3d2 hybridization, larger and weaker M-L bonds (higher energy) Inner orbital complexes d2sp3 hybridization, shorter and stronger M-L bonds (lower energy) Inner orbital complexes: Inert always Outer orbital complexes: Labile always
  • 6. Reaction through associative mechanism Outer orbital and inner orbital complexes with low lying unhybridized metal d-orbitals. These orbitals are center attack by the incoming ligand in associated mechanism of substitution. Inert complexes Electrons are present in the unhybridized d-orbitals. Labile complexes Vacant unhybridized d-orbitals. [MnCl6]3- = Labile [Cr(CN)6]3- = Inert d2sp3 XX XX XX XX XX XX XX XX XX XX XX XX sp3d2
  • 8.
  • 9.
  • 11. Dissociative mechanism: Square pyramidal intermediate Loss in CFSE = CFSE of SP – CFSE of Oh Associate mechanism: Pentagonal bipyramidal transition state Loss in CFSE = CFSE of PBP – CFSE of Oh If the loss in CFSE negative = inert complex If the loss in CFSE positive or zero = labile complex Basolo and Pearson calculated CFSE for LS and HS square pyramidal and pentagonal bipyramidal complexes.