CHAPTER 6

BONDING IN COMPLEX IONS

FACULTY OF APPLIED SCIENCES

UiTM PAHANG
 BONDING IN COMPLEX ION

 Metal to ligand bonds formed when a filled orbital of a ligands

overlaps with an empty hybrid orbital on the central metal atom.

 The molecular geometry is predicted using VSEPR.

 BONDING IN COMPLEX ION

 Strong field ligand will caused the d electron to be paired up.

 Weak field ligand will not caused the d electron to be paired up.

I-< Br -< Cl- < F- <OH- < C2O42- < H2O < SCN-<NH3 <en < NO2-< CN-<CO
WEAK STRONG
STRONG LIGAND WEAK LIGAND
CN- I-
-
NO2 Br-
CO Cl-
en (ethylenediamine) F-
-2
NH3 C2O4
H2O
OH-
 VBT: sp3 - outer shell hybridization

Four Coordinate Compounds (Tetrahedral Complexes)

Consider: [CoCl4]2-

Oxidation no of metal : Co + (-1 x 4) = -2

Co = +2

Electron configuration : Co = [Ar] 3d7 4s2

Co2+ = [Ar] 3d7

Since Cl is a weak field

ligand, 3d electrons
are not paired up.

Co2+ = [Ar] ↑ ↓ ↑↓ ↑ ↑ ↑ X X X X Since there are 4 ligands

surround the central metal atom.
3d 4s 4p

hybridization

[Ar] ↑ ↓ ↑↓ ↑ ↑ ↑ ↑↓ ↑ ↓ ↑↓ ↑↓

3d sp3
 VBT: dsp2 - inner shell hybridization

Four Coordinate Compounds (Square Planar Complexes)

Consider: [Ni(CN)4]2-

Oxidation no of metal : Ni + (-1 x 4) = -2

Ni = +2

Electron configuration : Ni = [Ar] 3d8 4s2

Ni2+ = [Ar] 3d8

Ni2+ = [Ar] ↑ ↓ ↑↓ ↑ ↓ ↑ ↑

3d 4s 4p
Since CN- is a strong field ligand, it
caused the pairing of unpaired 3d
electron.
Since there are 4 ligands
[Ar] ↑↓ ↑↓ ↑↓ ↑↓ X X surround the central
4s
X 4pX metal atom
3d
hybridization

[Ar] ↑ ↓ ↑ ↓ ↑↓ ↑↓ ↑↓ ↑ ↓ ↑↓ ↑↓
3d dsp2
 VBT: sp3d2 - outer shell hybridization

Six Coordinate Compounds (Octahedral Complexes)

Consider: [Fe(H2O)6] 3+

Oxidation no of metal : Fe + (0 x 6) = +3
Fe = +3

Electron configuration : Fe = [Ar] 3d6 4s2

Fe3+ = [Ar] 3d5

Since H2O is a weak

Since there are 6 ligands surround
field ligand, 3d
the
electrons are not
paired up. central metal atom.
Fe3+ = [Ar] ↑ ↑ ↑ ↑ ↑ X X X X X X
3d 4s 4p 4d
hybridization

[Ar] ↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑ ↓ ↑ ↓ ↑↓

3d sp3d2
 VBT: d2sp3 - inner shell hybridization

Six Coordinate Compounds (Octahedral Complexes)

Consider: [FeCN6]3-

Oxidation no of metal : Fe + (-1 x 6) = -3

Ni = +3

Electron configuration : Fe = [Ar] 3d6 4s2

Fe3+ = [Ar] 3d5

Fe3+ = [Ar] ↑ ↑ ↑ ↑ ↑

3d 4s 4p
Since CN- is a strong field ligand, it
caused the pairing of unpaired 3d
electron.
Since there are 6 ligands
[Ar] ↑↓ ↑↓ ↑ X X X X surround the central
4s
X metal atom
3d 4p
X
hybridization

[Ar] ↑↓ ↑ ↓ ↑ ↑↓ ↑ ↓ ↑↓ ↑↓ ↑↓ ↑↓
3d d2sp3
 CRYSTAL FIELD THEORY

 Explains that the bonding on complex ion purely in term

of electrostatic forces.
 Two types of electrostatic interaction involve.
 Attraction between the positive metal ion & negatively
charged ligands.
 Electrostatic repulsion between the lone pair on the
ligands & the electron in the d orbitals of the metals.
CRYSTAL FIELD THEORY
(OCTAHEDRAL)
 CRYSTAL FIELD THEORY
(OCTAHEDRAL)
 Central metal atom surrounded by six electron lone pair (ligands).

 So all five d orbitals experience electrostatic repulsion.

 The magnitude of repulsion depends on the orientation of d orbital involved.

 dx2-y2 & dz2 : the lobes point toward where the lone pair located.
- Thus it would experience greater lone pair – d orbital electron repulsion.

 They will be higher in energy.

 Thus, 5d orbitals are split between two sets of energy level.

• t2g set of orbitals (dxz, dyz, dxy) – lower in energy

• eg set of orbitals (dz2 , dx2-y2 ) – higher in energy

 CRYSTAL FIELD THEORY
(OCTAHEDRAL)
High energy
eg

Crystal field splitting

Lower energy
d-orbitals
t2g

 ∆ = energy difference between two sets of d orbitals in a metal atom

when ligands are present.
 Has direct effect on color & magnetic properties of complex ion.
CRYSTAL FIELD THEORY
(TETRAHEDRAL)
 CRYSTAL FIELD THEORY
(TETRAHEDRAL)
 Central metal atom surrounded by four electron lone pair (ligands).

 The d orbitals of tetrahedral complexes also split into two groups.

 The dxy, dyz, and dxz orbital point in the direction of the ligands. They will be
higher in energy than the degenerate orbitals of the free metal atom or ion.

 The dz² and dx²-y² orbitals point between the ligands thus are lower in energy.

 Thus, 5d orbitals are split between two sets of energy level.

• t2g set of orbitals (dxz, dyz, dxy) – higher in energy

• eg set of orbitals (dz2 , dx2-y2 ) – lower in energy

CRYSTAL FIELD THEORY
(TETRAHEDRAL)

High energy t2g

d-orbitals

eg

Lower energy
 CRYSTAL FIELD THEORY
(SQUARE PLANAR)
 There are four ligands as well.
 The difference is that the electrons of the ligands are only attracted to the plane.
 There are four different energy levels for the square planar.
 Strong Field Ligand
vs
Weak Field Ligands

Strong Field Ligand Weak Field Ligand

 The electrons of the metal ion pair in  The electrons will occupy all five
the lower energy t2g orbitals. orbitals before pairing occurs.

 Can be low spin - have few  Can be high spin - have more
unpaired electrons. unpaired electrons.

↑ ↑ eg
eg
Energy

Energy
∆ large ∆ small
↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↑
t2g t2g
 PROBLEM:

Iron forms an essential complex in hemoglobin. For each of the two

octahedral complex ions [Fe(H2O)6]2+ and [Fe(CN)6]4-, draw an orbital
splitting diagram, predict the number of unpaired electrons, and identify
the ion as low or high spin.

1) Identify oxidation number of transition metal.

2) Identify type of ligands (strong or weak).
3) Fill electrons in the d orbital.
[Fe(H2O)6]2+ = weak ligand [Fe(CN)6]4-= strong ligand

Fe + (0)6 = +2 Fe + (-1)6 = -4
Fe = +2 Fe = +2

Fe26 = [Ar] ↑ ↓ ↑ ↓ ↑ ↑ ↑ ↑
4s 3d

Fe26 = [Ar] ↑ ↓ ↑ ↑ ↑ ↑
↑ ↓
3d
Fe2+ = [Ar]
4s

↑ ↓ ↑ ↑ ↑ ↑

↑ ↑ eg 3d eg

Energy
Energy

∆ small ∆ large
↑ ↓ ↑ ↑ ↑ ↓ ↑ ↓ ↑ ↓
t2g t2g

 4 unpaired electrons  0 unpaired electron

 High spin  Low spin
 COLOR

 Many transition metal compounds absorb visible light in a process

that promotes a d electron from lower-energy d orbitals to higher-
energy d orbitals.

 Color in transition metal complexes is due to an electron being

excited from one d-orbital to a higher-energy d-orbital.

 These electronic transitions are called d–d transitions.

 A color of a substance appear when it absorb visible light at certain

wavelength.

 Color observed = complementary color of color absorbed.

 If no visible light been absorb, it appear as white or colorless.

 COLOR

400 nm 700 nm

higher energy lower energy

absorbed color observed color

 COLOR

 Different complexes exhibit different colors because color of light

absorbed depends on .

 Magnitude of  depends on:

 Ligand (Strong or weak field ligands)

- The amount of d-orbital splitting depends on the
ligands.
- Thus different ligands have different splitting
energies, and different colors result.

 Metal
 COLOR

Low light energy High light energy

 Example:

Why is an aqueous solution of Ni(NH3)6 2+ deep blue while an

aqueous solution of Ni(H2O)62+ is green. 3 6

 Ni(NH3)62+ contain stronger ligand. Therefore will have larger ∆.

 Large ∆ will absorb light with higher energy and shorter wavelength.
 Ni(NH3)62+ are blue because the compound absorbs higher-energy
(yellow) light.

 Ni(H2O)6 2+contain weaker ligand. Therefore will have smaller ∆.

 Small ∆ will absorb light with lower energy and longer wavelength.
 Ni(NH3)62+ are green because the compound absorbs lower-
energy (red) light.
 MAGNETISM

 Have to refer to the VBT & CFT.

 Low-spin complexes contain more paired electrons so, are more often
diamagnetic or weakly paramagnetic.

 Likewise, high-spin complexes usually contain more unpaired

electrons thus, are often paramagnetic.
↑ ↑ eg
eg
Energy

Energy
∆ large ∆ small
↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↑
t2g t2g

diamagnetic paramagnetic
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