Lecture

CHM102A
Gurunath Ramanathan
gurunath@iitk.ac.in +7417

Lecture 4
In lecture 3 we covered
Crystal eld spliIng of d-orbitals in Octahedral/ Tetrahedral complexes High spin-Low spin complexes Jahn-Teller eect Today we will cover Crystal eld theory of square planar complexes, magneUsm and spectra
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Jahn-Teller distorUon
If both the eg orbitals are symmetrically lled - all ligands are repelled equally. Result: regular octahedron If asymmetrically lled - some ligands are repelled more than the other . Result: Distorted octahedron repelled by 4 ligands- dx2-y2 is lled! repelled by 2 ligands if dz2 is lled! dz2 d1 dx2-y2 For z- in complexes (compression) dxz dyz

dxy

Special case of d8
d8 Ni(II), Pd(II), Pt(II), Cu(III), Ag(III) and Au(III)

2 u.e.

2 u.e.

The electrons in dz2 and dx2-y2 orbitals are repelled by the incoming ligands parUcularly more so when o is high.

DistorUon can ensure pairing of electrons in dz2 orbital but even with z out complexes there is sucient repulsion. Thus these ions prefer square planar geometry (C.No. 4) when o is high

Crystal Field Theory

Square planar eld

SP

Note: Consider only the orbitals!

Octahedral, Tetrahedral & Square Planar

dx2-y2 dz2 dxy dyz dxz

dx2-y2 dxy dz2

dxy dyz dxz

Pairing energy Vs. Weak eld < P Strong eld > P

dx2-y2 dz2
Small High Spin

dx dyz
z Mostly d8 (Majority Low spin) Strong eld ligands 7 i.e., Pd2+, Pt2+, Ir+, Au3+

Which geometry is preferred?

FormaUon of more bonds oers more stability ligand-ligand repulsion (sterics) CFSE is higher for Octahedral as compared to Td geometry.

When to expect Td geometry?

Ligands are bulky Low oxidaUon state of metal ion CFSE is small (d2/d7) or zero (d0 d5 d10) Dierence of CFSE between octahedral and Tetrahedral geometries is small to be overcome (d1 and d 6 is 0.13 o; d2 and d7 is 0.27 o) )

Does CFSE exist? Ionic radius vs no. of d electrons for M2+

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Enthalpy of HydraUon of hexahydrate / laIce energy

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Spinels
AB2O4 where A is in +2 and B is in +3 oxidaUon state. Case of rubies! fcc array of O2- A- 1/8 of tetrahedral sites B- of octahedral sites MgAl2O4- spinel If M3+ has lower CFSE than M2+ in Octahedral sites then inverse spinel is formed If M3+ has higher CFSE than M2+ in Octahedral sites then normal spinel results Fe3O4- +3 and +2 Fe (II) - d6 t2g4eg2, CFSE is - 0.4 o/ -0.6 t Fe(III) - d5 high spin, CFSE is 0 Inverse spinel

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Spinel CFT
Calculate for ruby, Mn3O4, MnCr2O4, and FeCr2O4 yourself!

ApplicaUons of CFT
MagneUsm Color

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Magne4c proper4es of metal complexes

DiamagneUc complexes very small repulsive interacUon with external magneUc eld no unpaired electrons

ParamagneUc complexes apracUve interacUon with external magneUc eld some unpaired electrons

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Measured magneUc moments include contribuUons from both spin and orbital spin. In the rst transiUon series complexes the orbital contribuUon is small and usually ignored.

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Electronic conguraUons of dn complexes from paramagneUsm and diamagneUsm Magnet on: ParamagneUc

Magnet o

Magnet on: diamagneUc

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MagneIc properIes
MagneIc suscepIbility () and the spin-only formula. Materials that are diamagneUc are repelled by a magneUc eld, whereas paramagneUc substances are apracted into a magneUc eld, i.e. show magneUc suscepUbility. The spinning of unpaired electrons in paramagneUc complexes of d-block metal ions creates a magneUc eld, and these spinning electrons are in eect small magnets. The magneUc suscepUbility, , due to the spinning of the electrons is given by the spin-only formula: (spin-only)

n(n + 2)

Where n = number of unpaired electrons.

MagneIc properIes
The spin-only formula applies reasonably well to metal ions from the rst
row of transiUon metals: (units = B,, Bohr-magnetons, 9.274 x 10-24 J/T)

Metal ion dn conguraUon e(spin only) e (observed) Ca2+, Sc3+ d0 0 0 Ti3+ d1 1.73 1.7-1.8 V3+ d2 2.83 2.8-3.1 V2+, Cr3+ d3 3.87 3.7-3.9 Cr2+, Mn3+ d4 4.90 4.8-4.9 Mn2+, Fe3+ d5 5.92 5.7-6.0 Fe2+, Co3+ d6 4.90 5.0-5.6 Co2+ d7 3.87 4.3-5.2 Ni2+ d8 2.83 2.9-3.9 Cu2+ d9 1.73 1.9-2.1 Zn2+, Ga3+ d10 0 0

Example:
What is the magneUc suscepUbility of [CoF6]3-, assuming

that the spin-only formula will apply:

[CoF6]3- is high spin Co(III). (you should know this). High- spin Co(III) is d6 with four unpaired electrons, so n = 4. We have eff = = 4.90 B n(n + 2) (5.3 obs)

energy

eg

t2g
high spin d6 Co(III)

Crystal Field SpliIng of d orbitals: high spin and low spin situaUons for a d6 metal Ligand strength: (Weak) I- < F- < H2O < NH3 < CN- (Strong)

Low spin Electrons spin pair

Large spliIng

Net unpaired spins = 0: DiamagneUc

High spin Electrons do Not spin pair

Small spliIng

Net unpaired spins = 4: Strongly paramagneUc

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How many unpaired spins in [Fe(CN)6]4- and in [Fe(H2O)6]2+?

What is the charge of Fe in [Fe(CN)6]4- and in [Fe(H2O)6]2+? Fe2+ in both cases Fe = [Ar]3d64s2; Fe2+ = [Ar]3d6 CN- is a strong eld ligand and H2O is a weak eld ligand
Energy gap larger than advantage due to Hunds rule

What kind of ligands are CN- and H2O?

Large spliIng Low spin

s = 0 BM Small spliIng High spin Energy gap small; Hunds rule applies s = 4.9BM
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How to calculate ?

Record UV-Vis spectra Ti3+ d 1

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Crystal Field Theory: The Color of CoordinaUon Compounds

The energy gap between the eg and t2g orbitals, 0, (the crystal eld spliIng) equals the energy of a photon: 0 = h = E h =

As 0, varies, h will also vary and the color of the compound will change

AbsorpUon of a photon causes a jump from a t2g to any eg orbital

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 [CrF6]3- [Cr(H2O)6]3+ [Cr(NH3)6]3+ [Cr(CN)6]3-

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Ligand subsUtuUons and color changes: Ni2+

H2O H2O Ni H2O H2O Green H2O H2O NH3

NH3
Ammonia

H3N Ni H3N NH3 Blue

NH3 NH3

en

en

Ethylene Diamine

en en Ni en en Purple en en dmgl dmgl Dimethyl glyoxime dmgl dmgl

dmgl dmgl Ni dmgl dmgl Pink

KCN
Potassium Cyanide

CN NC Ni NC CN Yellow
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CN CN

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AbsorpUon and ReecUon

Numbers are nm

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The spectrochemical series

For a given ligand, the color depends on the oxidaUon 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 WEAKER FIELD SMALLER LONGER STRONGER FIELD LARGER SHORTER

Copyright The McGraw-Hill Companies, Inc. Permission required for reproducUon or display.

[Fe(H2O)6]3+

[Ni(H2O)6]2+

[Co(H2O)6]2+

[Zn(H2O)6]2+ [Cu(H2O)6]2+
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The spectrochemical series of color and magneUc properUes: weak eld (red, high spin), strong eld (violet, low spin)
Spectrochemical series A d5 electron metal ion

Strong eld Ligands (violet, low spin)

Weak eld Ligands (red, high spin)

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absorpUon

Color of complexes depend on the value of 0 = h = E

0 = h

red absorpUon looks green

violet absorpUon looks yellow

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Crystal Field SpliIng of d- orbitals: high spin and low spin situaUons for a d5 metal (why are some complexes weakly colored?)

Color corresponds to the absorpUon of light an transiUons between d orbitals for metals. The transiUon for (b) is spin forbidden (s0) because an electron would need to ip its spin in being excited from a t orbital to a e orbital Colorless or very weakly colored
Spin selecUon rule s=0 is allowed Why?
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Colored

VisualizaUon of color as transmiped light which is not absorbed and the brains percepUon of mixed colored

In real systems there are regions of dierent light absorpUons leading to a wide range of colors

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Crystal Field Theory

400! 500! 600! 800!

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Spectra in complexes
d-d transiUons or ligand eld spectra Ligand to metal charge transfer Metal to ligand charge transfer Intraligand transiUons