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CHEM F111 Lecture 40:

Coordination Chemistry

What did we study so far?

Types of addition products: double salts and complexes

Primary and secondary valencies of complexes

Chemical reactions, conductometric and cryoscipic measurements for analysing complexes

Dipole moment, magnetic moment, electronic spectra Effective atomic number

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Valence bond theory

Hybridization A Mathematical manipulation; Useful to visualize certain aspects of bonding; Hybrid orbitals are hypothetical; non-existent; Hybrid orbitals can not be spectroscopically identified.

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Valence bond theory

Orientation of hybrid orbitals is dependent on the coefficients of the pure orbitals in their formation. e.g. consider [Cr (NH3)6]3+ Cr:Z= 24 (Ar, 3d5, 4s1) ; Cr3+ : 3d3

X = Pair of electrons from ligand Ligand electrons are placed in d2sp3 hybrid orbitals ==> octahedral shape 3 unpaired electrons; paramagnetic

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Valence bond theory

[CoF6]3-: Co3+ :3d6 ==>

The complex is paramagnetic and has octahedral shape. No vacant 3d orbital! How will the hybridization take place? Pauling's suggestion: The 4s, three 4p and two 4d orbitals mix to give sp3d2 hybridization==>octahedral

Outer orbital complex!

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Valence bond theory

[Co(NH3)6]3+: Co3+ : 3d6 This complex is found to be diamagnetic. ==> All electrons must be paired. Pauling's suggestion: The four unpaired electrons in 3d subshell pair-up to give two vacant 3d orbitals available for mixing with 4s and three 4p orbitals==>d2sp3 hybridization

Inner orbital complex!

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Valence bond theory

Outer orbital complex High-spin complex Spin-free complex Less stable (labile) Inner-orbital complex Low-spin complex Spin-paired complex Comparatively more stable

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Valence bond theory

[FeIII Cl4]Fe : Z=26 (Ar, 3d6, 4s2) ; Fe3+ : 3d5 5 unpaired electrons; paramagnetic

Ligand electrons are placed in sp3 hybrid orbitals Tetrahedral shape

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Valence bond theory

[Ni (CN)4]
II 2-

Ni: Z= 28 (Ar, 3d8, 4s2) ; Ni2+ : 3d8 No unpaired electrons; diamagnetic

Ligand electrons are placed in dsp2 hybrid orbitals Square Planar shape

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Limitations of VB theory
1.To predict the hybridization scheme one has to take aid of experimental results such as magnetic moment. 2. The method does not explain the extent of electron-pairing. 3. The method does not explain the colour and spectra of the coordination compounds. 4. Variation of magnetic moment with temperature can not be explained.

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Crystal field theory

1930-1940 Van Vleck, Bethe and others. Metal ligand attractions are electrostatic in nature. Even neutral ligands such as NH3 are of dipolar nature and the ve end is attracted to the electropositive metal.

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Crystal field theory

CFT is based on ionic model Ligands are treated as point charges Augmentations to account for covalency between metal and ligand by or type overlap resulted in Ligand Field Theory (LFT). The degeneracy of orbitals of metal atom (d orbitals in case of transition metal complexes) is destroyed when the ligands approach the metal ion to form coordinate bonds. <=== Symmetry consideration

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Crystal field theory

Symmetry consideration: Two sets of d-orbitals

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CFT: Octahedral complexes

When the ligands approach the metal ion along the coordinate axes, the perturbation on dz2 and dx2-y2 is greater than the dxy, dyz and dzx orbitals.

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CFT: Octahedral complexes

Degeneracy of d-orbitals breaks: The level of d-orbitals splits into two sets: t2g and eg

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CFT: Octahedral complexes

eg orbitals (dz2 and dx2-y2) are along Inter Nuclear Axes (INA) (Metal-Ligand bond axes) : more repulsion : high energy t2g orbitals (dxy , dyz , dzx) are away from Inter Nuclear Axis (INA) (Metal-Ligand bond axes): less repulsion : low energy We dont refer to isolated metal atom/ion any more; The weighted mean of these two levels is assumed to be zero and is called Bari center. oct = o = 10 Dq (different notations for the splitting)

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CFT: Octahedral complexes

6Dq = 0.6 o 4Dq = 0.4 o How to calculate o? Electronic spectra Born-Harber cycle based lattice energies

1kJmol-1 = 83.7 cm-1

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CFT: Octahedral complexes

Consider [Ti(H2O)6]3+, Ti3+: 3d1 Consider t2g eg transition __ __ eg __ __

__ __ __ t2g

__ __ __

Thus o = 20,300/83.7 = 243 kJmol-1 for [Ti(H2O)6]3+; The complex is reddish violet in colour; actually yellow and green light are absorbed and hence the complementary colour (reddish violet ) is seen.
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CFT: Octahedral complexes

In the d1 system one electron is in the orbital with energy 0.4 o below the Bari Centre. This complex is stabilized w.r.t. spherically symmetric field by 0.4 o. In general, for an octahedral complex, we define Crystal Field Stabilization Energy = CFSE = (-0.4nt2g + 0.6 neg) o ; n= no. of electrons Thus for [Ti(H2O)6]3+ we have CFSE = -0.4 x 1 x o =-0.4x243 = -97 kJ mol-1 NOTE: This stability is w.r.t. Bari Centre.
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