5/4/2009

• Definitions
– an example

• Werner’s Theory of Complexes
– his experimental results

• Types of Ligands

• Valance Bond Theory

• Chrystal Field Theory

• Ligand Field Theory
– ligand sigma and pi  bonding

–Jahn‐Teller distortion

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• Ligands
[Ag(NH3)2]+
– an ion or molecule which donates electron
density to a metal atom /ion to form a complex
Lewis base
• Coordination  Complex ligand
– a  central metal atom/ion  and  its set of ligands

– often  an ion  itself

• Coordination Compounds
– a  neutral  species made up in some part of a 
complex
p

– often the salt of a coordination complex Lewis acid
• Coordination Number
– the number of ligands in the primary or inner 
shell of ligands

Example Mol. Formula Lewis base Lewis acid Donor atom Coordination #

[Ag(NH3)2]+ NH3 Ag+ N 2

[Zn(CN)4]2‐ CN‐ Zn2+ C 4

[Ni(CN)4]2‐ CN‐ Ni2+ C 4

[PtCl6]2‐
2 Cl‐ Pt4+ Cl 6

[Ni(NH3)6]2+ NH3 Ni2+ N 6

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Praseo Luteo
[CoCl3(NH3)4]s [CoCl3(NH3)6]s
Purpureo Releo
Green Yellow/Orange
[CoCl3(NH3)5]s [CoCl3(NH3)5 H2O]s
Purple Red

Ag+ (aq) + Cl‐ (aq) → AgCl (s)

What happens when excess Ag+ ion is added to the solution ?

[CoCl3(NH3)6]s
Three moles of AgCl are formed for each mole of                                       and [CoCl3(NH3)5 H2O]s
complex in the solution.

[CoCl3(NH3)5]s
However, only two of the Cl‐ ions in the                                     and only one of the Cl ‐ ions in 
[CoCl3(NH3)4]s
can be predicated with Ag+ ions.

[CoCl3(NH3)6]s
Conductivity of aqueous solutions suggest that the                                         and [CoCl3(NH3)5 H2O]s

complexes dissociate in water to give a total of four ions. 

[CoCl3(NH3)5]s dissociates to give three ions, 

[CoCl3(NH3)4]s dissociates  to give only two ions.

Why?

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Co3+ ion have a primary valence and a secondary valence. The primary valence is the number of
negative ions needed to satisfy the charge on the metal ion. In each of the cobalt(III) complexes previously
described, three Cl‐ ions are needed to satisfy the primary valence of the Co3+ ion.

The secondary valence is the number of ions of molecules that are coordinated to the metal ion.
Werner assumed that the secondary valence of the transition metal in these cobalt(III) complexes is six.

[CoCl3(NH3)4]s [CoCl3(NH3)5]s [CoCl3(NH3)6]s [CoCl3(NH3)5 H2O]s

Monodentate Ligands
Monodentate ligands are Lewis bases that donate a single pair ("mono") of electrons to a metal
atom. Monodentate ligands can be either ions (usually anions) or neutral molecules.

Ligand Structure Name Ligand Structure Name

I‐ iodide ion Br‐ bromide ion

F‐ fluoride ion Cl‐ chloride ion

OH‐ hydroxide ion CO car. monoxide

CN‐ cyanide ion SCN‐ thiocyanate ion

H2O water NH3 ammonia

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Bidentate Ligands
Bidentate ligands are Lewis bases that donate two pairs ("bi") of electrons to a metal atom.

Name Structure Name Structure

oxalate ion phenanthroline

acetylacetonate
ethylenediammine
ion

[C (NH3)4(H2O)2]2+
[Cu(NH

[Cr(ox)3]3‐

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Electron configuration of the transition‐ metal ion
Co3+: [Ar] 3d6

Valence‐shell orbitals

Co3+: [Ar] 3d6 4s0 4p0

3d electrons in the dxy, dxz, and dyz orbitals in this subshell

The 3dx2‐y2, 3d
The 3d 3dz2, 4s, 4p
4s 4px, 4p
4py and 4p are then mixed to form a set of empty d2sp3 orbital that point 
and 4pz orbitals are then mixed to form a set of empty d orbital that point
toward the corners of an octahedron. 

Hybridization Orbitals Molecular Geometry

sp
p Linear

sp2 Trigonal Planar

sp3 Tetrahedral

sp3d Trigonal Bipyramidal

sp3d2 Octahedral 

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The crystal field model concentrates on the splitting of the d orbitals of the transition metal atom 
into groups as a result of electrostatic interactions between the ligands and the electrons in the unhybridized
orbitals of the transition metal atom. 

[MnCl6]4‐
hexachloromanganate(II) ion
The model can be used to understand, interpret and predict the magnetic behavior, colors and 
some structures of coordination complexes..

Two of the 3d orbitals (3dx2‐y2 and 3dz2) on the Mn2+ ion point directly toward the six Cl1‐ ions, as shown in the 

figure below. 
eg

t2g
The other three orbitals (3dxy, 3dxz, and 3dyz) lie between the Cl1‐ ions.

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Crystal Field Theory: Simple ionic model, does not accurately describe why the orbitals are
raised or lowered in energy upon covalent bonding.

LFT uses Molecular Orbital Theory to derive the ordering of orbitals within metal complexes.

Same as previous use of MO theory, build ligand group orbitals, combine them with metal
atomic orbitals of matching symmetry to form MO’s.

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Anti‐bonding orbital

Atom A Atom B

large perturbation Bonding orbital

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• The reducible representation: G = A1g +  T1u +  Eg

• Nondbonding metal orbitals:  dxy, dxz, dyz orbitals
have T2g symmetry.
• Bonding metal orbitals: s orbital has A1g symmetry; 
px, py, pz have T1u symmetry, and dx2‐y2, dz2, have Eg sym.

• The 6 metal AO’s of proper symmetry combine with 
the six ligand group orbitals.

• 6 bonding MO’s are filled by ligand electron pairs

• The metal t2g Atomic Orbitals are nonbonding (dxy, 

dxz, dyz)

• 6 antibonding orbitals are formed with the same 

symmetries as the bonding orbitals

• The 2 eg* antibonding orbitals are the lowest 

energy antibonding orbitals available

• The d‐electrons from the metal ion will fill in the t2g
and eg* MO’s

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• Interactions occur between frontier metal orbitals and the pi orbitals of L

• Two types depends on the ligand
–pi
pi acid ‐
acid ‐ back bonding accepts e‐
back bonding accepts e‐ density from M
density from M
–pi base ‐additional e‐ density donation to the M
• Type of bonding depends on relative energy level of pi orbitals on the ligand and the metal orbitals

Basic Acidic

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[μmag=n(n+2)0.5μB] 

[
[n:unpaired electron] 
i d l t ]

The Jahn‐Teller (J‐T) theorem states that in molecules/ ions that have a degenerate ground‐
state, the molecule/ion will distort to remove the degeneracy.

Stretching of the two atoms in z‐direction in an octahedron leads to an advantage for all 
orbitals with z‐components because the repulsion decreases. 

Splitting of the two energetic levels into four levels at all 

Complexes with unsymmetric occupation of the higher level d‐orbitals often show 

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All six Cu‐O bonds two long axial Cu‐O 
equal at 2.05 Å bonds = 2.45 Å

[Cu(H2O)6]2+ four short Cu‐O 
no J‐T distortion bonds = 2.00 Å

Increasing bond length of Oh

dx2-yy2

eg
energy

dz2

dxy

t2g

Cu(II) in regular Oh dxz dyz

Cu(II) after J‐T distortion

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1. http://www.trentu.ca/chemistry/chem321h/lectures/lecture‐321coordination_compounds.pdf

2. http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch12/complex.php#typical

3. http://symmetry.jacobs‐university.de/cgi‐bin/group.cgi?group=904&option=4

4. faculty.swosu.edu/tim.hubin/InorganicLects/InorgCh10.2.ppt

5. www.uncwil.edu/chem/Courses/Hancock/CHM445/documents/Chemistry445lecture17J‐
TdistortionandCN4.ppt

6. Molecular Quantum Mechanics, P. W. Atkins, R. S. Friedman

7. http://en.wikipedia.org/wiki/Crystal_field_theory

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