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Lewis Acid/Base Reactions

Lewis acid-base theory describes metal-ligand bonding in coordination complexes. A Lewis acid is an electron pair acceptor, such as a metal ion, while a ligand is a Lewis base that donates an electron pair. Valence bond theory models the bonding using hybridized metal orbitals that overlap with ligand orbitals. Crystal field theory explains color and magnetic properties using the electrostatic interaction between ligands and the metal's d-orbitals. Ligands create an electric field that splits the d-orbitals, determined by factors like the ligand and its strength in the spectrochemical series.

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52 views9 pages

Lewis Acid/Base Reactions

Lewis acid-base theory describes metal-ligand bonding in coordination complexes. A Lewis acid is an electron pair acceptor, such as a metal ion, while a ligand is a Lewis base that donates an electron pair. Valence bond theory models the bonding using hybridized metal orbitals that overlap with ligand orbitals. Crystal field theory explains color and magnetic properties using the electrostatic interaction between ligands and the metal's d-orbitals. Ligands create an electric field that splits the d-orbitals, determined by factors like the ligand and its strength in the spectrochemical series.

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Lewis Acid Base Theory

➢ Gilbert N. Lewis, 1920s


❖ Lewis Acid/Base reactions:
Lewis Base:→ electron pair donor
Lewis Acid ←:electron pair acceptor
❖ Ligands: Lewis bases
❖ Metals: Lewis acids
❖ Metal Complexes - Formation of a complex
was described as an acid – base reaction
according to Lewis

Sidgwick’s Effective atomic number (EAN) rule is based on the Octet theory of Lewis and this
❑ Sidgwick’s is the first attempt to account for the bonding in complexes. The metal ion in a coordination
Rule: complex will continue accepting the electrons till the total number of electrons in the metal
ion becomes equal to the atomic number of the noble gas of that series.
Valence Bond Theory

➢ Linus Pauling, 1931


➢ Valence bond theory predicts that
the bonding in a metal complex
arises from overlap of filled ligand
orbitals and vacant metal orbitals.
● Central metal atom provides the empty
orbitals equal to its coordination number
● Empty orbitals hybridise to provide equal
number of hybridised orbitals that can
overlap with the orbital of ligands
Valence Bond Theory

➢ Tetrahedral Geometry

[CuCl4]2-
3d 4s 4p

Cu in ground state (3d94s2)

Cu+2 ion

Cu+2 in [CuCl4]2- sp3 (4 e– pairs by Cl– ions)


 One unpaired electron: Paramagnetic
Valence Bond Theory

➢ Tetrahedral Geometry ➢ Square Planar Geometry

[Ni(CN)4]2-

[CuCl4]2-
3d 4s 4p
3d 4s 4p

Cu in ground state (3d94s2) Ni in ground state (3d84s2)

Cu+2 ion Ni2+ ion

[Ni(CN)4]2-
Cu+2 in [CuCl4]2- sp3 (4 e– pairs by Cl– ions) dsp2 (4 e– pairs by CN– ions)
 One unpaired electron: Paramagnetic
 All paired electrons: Diamagnetic
Valence Bond Theory
➢ Octahedral Geometry
[CoF6]3– : Octahedral cobalt complex
3d 4s 4p 4d [Fe(CN)6]3-

3d 4s 4p
Co in ground state (3d74s2)

Fe in ground state (3d64s2)


Co+3 ion

Fe+3 ion

Co+3 in [CoF6]3- sp3d2 (6 e– pairs by F– ions)

d2sp3 (6 e– pairs by CN– ions)


➢ it paramagnetic and is called a high-spin complex
Fe+3 in [Fe(CN)6]3-
➢ Paramagnetic
Valence Bond Theory

➢ Compounds of the complex ion [Co(CN)6]3- have no unpaired electrons, but


compounds of the [CoF6]3- ion have four unpaired electrons per metal ion

Crystal Field Theory (CFT)


➢ explain the breaking of degeneracies of electron orbitals (d/f orbitals) due to the
electric field produced by a surrounding ligand(s)
➢ bonding in a complex to be an electrostatic attraction between a +ve charged
nucleus and the electrons of the ligands.
Crystal Field Theory (CFT)
➢ the ligands to be negative points of charge that repel the electrons in the d orbitals of the metal ion.

0 crystal-field splitting energy

high spin: low spin: high spin: low spin: high spin: low spin:
weak-field ligand strong-field ligand weak-field ligand strong-field ligand
weak-field ligand strong-field ligand
Crystal Field Theory (CFT)

high spin: low spin: # Spectrochemical Series


weak-field ligand strong-field ligand
I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO

WEAKER FIELD STRONGER FIELD

 

 
SMALLER Δ0 LARGER Δ0

LONGER λ SHORTER λ

# Complexes of Co (III) show the shift in color due


0 (crystal-field splitting energy) depends on to the ligand: (a) CN–, (b) NO2–, (c) phen, (d) en,
 nature of ligands (e) NH3, (f) gly, (g) H2O, (h) ox2–, (i) CO3 2–
 Charge of the metal ion [Co(NH3)6]3+ > [Co(NH3)6]2+
 Metal ion and it’s d orbital
[Co(NH3)6]3+ = 23,000 cm-1 (3d)
[Rh(NH3)6]3+ = 34,000 cm-1 (4d)
[Ir(NH3)6]3+ = 41,000 cm-1 (5d)
Spectrochemical Series

➢ For a given ligand, the color depends on the oxidation state of the metal ion
➢ For a given metal ion, the color depends on the ligand
I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO

Increasing Δ0

[Cr(H2O)6]3+

❑ Ligand Field Theory (LFT) and the Molecular Orbital (MO) theory are considered sophisticated models as
compared to CFT.

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