Definition

A coordination complex or
metal complex, is an atom or ion
(usually metallic), bound to a
surrounding array of neutral
molecules, cations or anions, can
exist independent in solution
Coordination Complex’s structure
Complex compounds have: inner coordination sphere
and outer coordination sphere
Inner coordination sphere has: central metal ion and
ligands
Some coordination complex don’t have outer
coordination sphere.

Example 1: Na3[Fe(CN)6] includes:

*Inner coordination sphere: [Fe(CN)6]3-
*Outer coordination sphere: Na+
[Fe(CN)6]3- includes:
*Central metal ion: Fe3+
*Ligand: CN-
Coordination Complex’s structure
Example 2: [Cu(NH3)4](OH)2 includes:
* Inner coordination sphere: [Cu(NH3)4]2+
* Outer coordination sphere: OH-
[Cu(NH3)4]2+ includes:
* Central metal ion: Cu2+
* Ligand: NH3

Example 3: Fe(CO)5 doesn’t include outer

coordination sphere.
Fe(CO)5 includes:
* Central metal ion: Fe
* Ligand: CO
 Valence Bond Theory
Coordination complex are formed by
dative covalent bond between
central metal ion and ligands.
 The symmetric geometry of ligands
bounding central metal ion are
constructed by hybridization of covalent
orbital of central metal ion
 Valence Bond Theory
Hexafluoridocobaltate(III) compound
Geometry structure: octahedral
Magnetism: paramagnetic
Color: blue
 Valence Bond Theory
Hexafluorocabaltate (III) compound

Valence bond theory:

Electron
configuration
of Co3+

Electron
configuration
of Co3+ in
coordination sp3d2 hybridization
complex
 Valence Bond Theory
Hexaamminecobalt(III) compound
Geometry structure: octahedral
Magnetism: diamagnetic
Color: yellow
 Valence Bond Theory
Hexaamminecobalt(III) compound
Explanation:

Electron
configuration
of Co3+

Electron
configuration of
Co3+ in
coordination
complex d2sp3 hybridization
 Valence Bond Theory
Tetracarbonylnickel(0) compound
Geometry structure: tetrahedral
Magnetism: diamagnetic
Color: colorless
 Valence Bond Theory
Tetracarbonylnickel(0) compound
Explanation:

Electron
configuration
of Ni

Electron
configuration of
Ni in
coordination sp3 hybridization
complex
 Valence Bond Theory
Tetracloridonickelate(II)
Geometry structure: tetrahedral
Magnetism: paramagnetic
Color: colorless
 Valence Bond Theory
Tetracloridonickelate(II)
According to VB’s theory:

Electron
configuration
of Ni2+

Electron
configuration of
Ni2+ in
coordination sp3 hybridization
complex
 Valence Bond Theory
Tetracloridoplatinate(II)
Geometry structure: square planar
Magnetism: diamagnetic
Color: dark red
 Valence Bond Theory
Phức tetracloridoplatinat(II)
Giaûi thích theo thuyeát lieân keát hoùa trò:

Electron
configuration
of Pt2+

Electron
configuration of
Pt2+ in
coordination
complex dsp2 hybridization
 Valence Bond Theory

 Valence bond theory can explain

Coordination number of coordination
compounds.
Geometry structure of coordination
compounds.
Magnetic properties of coordination
compounds
 Some problems cannot be explained by using
Valance bond theory!
Other coordination compound is color while tetracarbonynickel
is colorless? Why?
 The distribution of hybrid orbital in space of Co(III) with
different ligands such as NH 3 and F- is different? [Co(NH3)6]3+
is called an inner orbital or low spin or spin paired complex
while [CoF6]3- is outer orbital or high spin or spin free complex.
 Similarly, [Ni(Co)4] is spin paired complex while [NiCl 4]2- is spin
free complex? Why?
Tetrachloridonickelate(II) and tetrachloridoplatinate(II)
compound have the same lignads but different geometry
structure?
Na[BF4], Na3[BF6]
Na3[Al(OH)6], Na[Al(OH)4]
 Crystal Fields Theory

Contents:
Coordination compounds are formed by the
electrostatic interactions between
central metal ion and ligands.
Electrostatic interactions between
central metal ion and ligands can change
the valence electron configuration of
central ions.
 Explain structure of octahedral coordination
compound by using Crystal Field Theory.
[CoF6]3-: Octahedral coordination compound, paramagnetic, light blue

Distribution on x, y, z axes of F-
ion surrounding Co3+ ions
Explain structure of octahedral coordination compound by using Crystal
Field Theory.

Electron configuration of Co3+ ion: 3d64s04d0

5 orbital 3d of Co3+ include:
Electron density of 2 orbital 3dx2-y2 and 3dz2
distribute on x, y and z axes.
Explain structure of octahedral coordination
compound by using Crystal Field Theory.

Electron density of 3 orbitals 3dxy, 3dyz and 3dxz

distribute on planar.
Explain structure of octahedral coordination
compound by using Crystal Field Theory.

The interaction between 2 orbital 3dx2-y2, 3dz2

and F- ions is stronger than the interactions of
3dxy, 3dyz and 3dxz. So, this leads to the splitting
of 5 d-orbital to 2 energy levels known as
crystal field splitting : d(eg) (include 3dx2-y2
and 3dz2) and d(t2g) (include 3dxy, 3dyz and 3dxz)
 d x2-y2 d z2
o
or
+ 6 Dq

o
or
- 4 Dq

dxy dyz dxz

Explain structure of octahedral coordination
compound by using Crystal Field Theory.

3 d-orbital splitting diagram of [CoF6]3-

Explain structure of octahedral coordination
compound by using Crystal Field Theory.
O = Edγ - Ed is crystal field splitting energy
O of [CoF6]3- is 1,61 eV.
Electrons adsorb energy from light (1,61eV)
and transmit from dε(t2g) to dγ(eg). Adsorbed
energy correspond to the energy of red wave
light, therefore, the color of
hexafluoridocobaltate(III) is light blue.
 Coordination compound’s color and The
Spectrochemical Series
Table 1
Wave length of Energy Adsorbed Color of
adsorbed (kJ/mol) color compound
light (nm)
400 – 435 299 – 274 Purple Green – yellow
435 – 480 274 – 249 Blue cyan Yellow
480 – 490 249 – 244 Indigo blue Orange
490 – 500 244 – 238 Light blue Red
500 – 560 238 – 214 Green Pink
560 - 580 214 - 206 Green-yellow Purple
560 – 595 206 – 200 Yellow Blue cyan
595 – 605 200 – 198 Orange Indigo blue
605 – 750 198 – 149 Red Light Blue
 Coordination compound’s color and The
Spectrochemical Series
According to table 1 and coordination
compound’s color, we can calculate value of
O.
The effect of ligand on O called The
Spectrochemical Series, ordered by the
descending of ’s value:
CO; CN- > NO2- > NH3 > NCS- > H2O > OH‑ >
> F‑ > SCN‑ > Cl- > Br- >I-
High spin and low spin coordination compound
Condition of pairing electron
The energy required to pair two
electrons in the same orbital is called
pairing energy (P).
In octahedral coordination compound, if
the number of valence electron >3 and <8:
If  >P  low spin complex
If  < P  high spin complex.
High spin and low spin coordination compound
  E OF OCTAHEDRAL COMPLEX IN LOW AND
HIGH SPIN CASES

dn High Low Spin dn High Low Spin

Spin Spin
d0 0 0 d6 -2/5O -12/5O+2EP

d1 -2/5O -2/5O d7 -4/5O -9/5O+EP

d2 -4/5O -4/5O d8 -6/5O -6/5O

d3 -6/5O -6/5O d9 -3/5O -3/5O

d4 -3/5O -8/5O+EP d10 0 0

d5 0 -10/5O+2EP
High spin and low spin coordination compound
Calculate Crystal Field Stabilization
Energy (CFSE) and magnetic properties of
CoF63- and Co(NH3)63+. Known that
splitting energies of CoF63- and Co(NH3)63+
are 155 and 273.2, respectively and pairing
energy is P(kJ/mol) = 250,5
Solution:
Magnetic properties:
Electron configuration of Co3+ is 3d6,
• CoF63- has  < P so that Co3+’s electron configuration is
d4d2 (according to CFT)
• High spin complex and paramagnetic.
High spin and low spin coordination compound

Co(NH3)63+ has  > P so that Co3+’s electron configuration is

d6 (according to CFT)
Low spin complex compound and diamagnetic.
High spin and low spin coordination compound

2) Calculate Crystal Field Stabilization Energy (CFSE)

High spin complex CoF63-:
E = 4(-2/5) + 23/5 = 2/5 =2/5155 = -62kJ/mol
Low spin complex Co(NH3)63+:
E = 6(-2/5) + 2P = -12/5 +2P = -154,68kJ/mol

Conclusion: Low spin complex is more stable than

high spin complex.
 Explain structure of tetrahedral
coordination compound by using CFT.
Tetrahedral complex compound [Cu(NH3)4]2+,
paramagnetic, sea blue.
 Explain structure of tetrahedral
coordination compound by using CFT.
According to the position of NH3 molecular to
Cu2+ ion, the electrons are attracted away from
the axes, this means that dxy, dxz, and dyz have
higher energy levels than dx2- y2 and dz2 (dγ)
Explain structure of tetrahedral coordination
compound by using CFT.

3 d-orbital split into 2 energy levels: d ε has

higher energy level than dγ
Explain structure of tetrahedral coordination
compound by using CFT.
Tetraamminecopper(II) has ∆T = 1,56V.
Electrons adsorb energy from light (1,56eV) and
transmit from dγ to dε. Adsorbed energy
correspond to the energy of red wave light,
therefore, the color of tetraaminecopper(II) is blue.

Caution: With the same central metal ion and

ligands, T  4/9O therefore, tetrahedral complex
compounds are high spin complex.
 CFT’s assessment
Advantages:
Can explain the rich of complex compound and color of
complex compound.
Established Spectrochemical series.
Can explain magnetic properties of coordination compound
(high spin and low spin coordination compound)
Disadvantages:
Cannot explain satisfactorily stability of complex
compounds, formed by valence bonds.
Cannot explain the properties of Spectrochemical series.
Molecular orbital theory for coordination compounds
Molecular orbital theory’s contents:
Molecule is as united structure, contents nuclei and a sets
of molecular orbitals.
Each electron in molecule has different condition and it
was described by a molecular orbital wave function.
Molecular electron shell is constructed by Linear
Combination Atomic Orbital (LCAO).
Atomic orbitals can be combined with others if they have
the same symmetry structure and a near energy level.
Coordination compound can be formed by the
degeneracy’s descending of subshells, containing lot of
orbital.
Electron configuration’s establishing methods
by applying Linear Combination of Atomic
Orbitals (LCAO)
a)Approving that valence atomic orbitals of central
metal ion are changed significantly to formed
molecule. Therefore, valence atomic orbitals can
only combine with other valence atomic orbitals
and another atomic orbitals become non-bonding
molecular orbitals (This means non-combined
orbitals, having the same energy level as atomic
orbitals, do not effect to the stability of molecule).
 LCAO method

b) Atomic orbitals, having the same symmetric

properties can only combine with each other.
c) Atomic orbital’s combination becomes more
easily if they have the close energy level and
large overlap regions.
d) The result of orbital’s combination must
follow this rule:
 a anti-
a AO of atom A bonding MOs E
ne
(b-a) non- rg
+ = bonding MOs
y
b AO of atom B
a Bonding le
MOs
ve
Assumed that a<b
l
Assessment about molecular orbital diagram of
octahedral coordination compound without π-
bonding ligands
CoF63- coordination compound
Space distribution of F- ions surrounding Co3+
ion:
Assessment about molecular orbital diagram of octahedral
coordination compound without π-bonding ligands

Orbital combination according to LCAO

method:
6 atomic orbital of Co3+: 4s , 4px , 4py , 4pz, 3dx2-y2
and 3dz2 with 6 2px atomic orbitals of 6 F- ions.
12 molecular orbitals are formed, including: 6
anti-bonding orbitals and 6 bonding orbitals.
Assessment about molecular orbital diagram of octahedral
coordination compound without π-bonding ligands

Example of Orbital combination:

The combination between 4s orbital of Co3+ and 6 2px
orbital of 6 F- ions
Assessment about molecular orbital diagram of octahedral
coordination compound without π-bonding ligands
Example of Orbital combination:
The combination between 4px orbital of Co3+ and
two 2px-orbital of 6 F- ions on x-axis
Assessment about molecular orbital diagram of octahedral
coordination compound without π-bonding ligands
Example of Orbital combination:
The combination between 4dx2-y2 orbital of Co3+ and four
2px-orbitals of 6 F- ions on x and y axes
Assessment about molecular orbital diagram of octahedral
coordination compound without π-bonding ligands
Besides the combined orbitals, Co3+ ion still
has 3 orbitals: 3dxy, 3dyz and 3dzx, these
orbital becomes  non-bonding orbital in set
of molecular orbitals.
Molecular orbital diagram of high-spin octahedral
coordination compound CoF63- and low-spin
octahedral coordination compound Co(NH3)63+ are
shown in next slide:
Assessment about molecular orbital diagram of octahedral
coordination compound without π-bonding ligands
Assessment about molecular orbital diagram of octahedral
coordination compound without π-bonding ligands
 Co(NH3)63+ is slow-spin coordination
compound (ms = 0), diamagnetic.
 CoF63- is high-spin coordination
compound (ms = +2), paramagnetic.
Crystal field splitting energy:
 = E*dγ - E0d
Assessment about molecular orbital diagram of octahedral
coordination compound without π-bonding ligands

Color of these coordination compounds is caused

by the transmit of electron from 0d to empty *dγ
orbital. (color of Co(NH3)63+ is yellow and CoF63- is
light blue)
Low-spin coordination compound Co(NH3)63+ is
more stable than high-spin coordination
compound CoF63- because the stability of dγ
bonding is higher *dγ and there is no electron on
*dγ
 Molecular orbital diagram of Octahedral
coordination complexes with π-bonding ligands
In the presence of pπ orbitals (bonding π orbitals)
cause the change in value of crystal field splitting
energy ∆.
-acceptor ligand:
Bonding π orbitals of ligands can combine with dε
of central metal ion, this leads to the increasing of ∆
and π0 becomes πbonding, containing electrons. It
means, coordination compound become more
stable.
 Molecular orbital diagram of Octahedral
coordination complexes with π-bonding ligands
-donor ligand
Bonding π orbitals of ligands combining with dε
of central metal ion, will cause the small ligand-
field splitting. However, the form of π bonding
leads to the increasing of coordination
compound’s stability in comparing with weak
field and non π bonding compound. In this
case, the smaller ligand-field splitting energy,
the more stability the compound is.
According to the Molecular orbital diagram of coordination
compound:
1)With non -bonding coordination compound, the high value
of  will lead to the higher stability of compound because of
the increasing of (dγ) bonding’s stability.
2) With -acceptor bonding coordination compound, the
high value of  will lead to the higher stability of
compound because of the low -bonding’s value.
3) With non -donor coordination compound, the low
value of  will lead to the higher stability of compound
because of the low -bonding’s value.
4)The value of  depend on the properties of ligands. This rule
can be used to explain the properties of spectrochemical
series:
-acceptor ligands > non -bonding ligands < -donor ligands
 Molecular orbital diagram of
octahedral coordination compound
Molecular orbital diagram of octahedral
coordination compound
Molecular orbital diagram of octahedral
coordination compound
 Molecular orbital diagram of octahedral
coordination compound
Assessment 4:
Properties of ligans lead to the increasing value of . This
rule can be used to explain the properties of
spectrochemical series:
-acceptor ligands > non -bonding ligands< -donor ligands