• Ruth Natalia

• Dinar Anugrah 1406344

• Rizka P. 1401464
Group 3 • Suci A. 1406080
• Elsa D. 1405206
• Aisyah D.I. 1401394
• Desi S. 1400931
• Alliefsa T. 1406315

• Milantika D.P. 1400932

Molecular Orbital Theory •

•
Ruslan F.
Ari N.F.
1406390
1400979
Limitation of molecular orbital
theory
Though it too has certain lilmitations:
1. Molecular orbital theory is based on quantum mechanical principles and
hence hard to conceive, especially for the beginners.
2. It does not give any idea of molecular geometry, shape etc.
3. Although it can successfully describe many a properties, explanation of all
the molecular properties or bonds is beyond its ambit. A combination of
VBT and MOT is required for a more complete understanding.
4. It becomes exceedingly cumbersome, if not impossible, to explain bonding
in polyatomic molecules on the light of mot alone.
 Molecular Orbital Theory

Bonding molecular orbitals are orbitals with

electron density approaching belt centered on the
area between the two nuclei are joined and thus
produce a more stable situation

Molecular Orbital is the

Antibonding molecular orbitals are orbitals with
result of overlapping and
electron density away from the central belt area
merging of atomic
between the nucleus together and produce a less
orbitals in a molecule.
stable situation.

nonbonding orbital molecular orbital that is what

happens when the area overlaps exist unreacted
atomic orbitals in bonding
Spectrochemical
Series
Spectrochemical series

– A spectrochemical series is a list of ligands ordered on ligand

strength and a list of metal ions based on oxidation number,
group and its identity.
– Measurement of the magnetic properties and the absorption
spectra of transition metal complexes can rate the weakest
ligand from interacting with the metal ion (thus giving the
smallest crystal field splitting) to the most powerful interact
and provide the greatest division
Spectrochemical series of ligands

– A partial spectrochemical series listing of ligands from small Δ to

large Δ is given below.
– O22−< I− < Br− < S2− < SCN− < Cl− < N3− < F−< NCO− < OH− < C2O42− ≈
H2O < NCS− < CH3CN < py (pyridine) < NH3 < en (ethylenediamine)
< bipy (2,2'-bipyridine) < phen (1,10-phenanthroline) < NO2− <
PPh3 < CN− ≈ CO
– The idea of the series is that the orbital separation d, and
hence the relative frequencies absorption bands of visible
light for the two complexes containing metal ions same
but different ligands, can be predicted from the series,
whatever certain metal ions earlier.
– The following requirements need to keep in mind in
applying it
1. Series based on data for the metal ions in the general level
of oxidation.
2. Even for the metal ions in the normal oxidation levels are
sometimes found a reversal of the sequence of members of
adjacent or nearly adjacent in the series
The strength of the Atomic ligand
shown by spectrochemical series

Factors that affect the atomic series:

1. The size of atoms / molecules, ex: compare F- and I-
2. The existence of the electron pair of non - bonding, ex: H2O and NH3
3. The existing of the back bonding
Backbonding
 Electroneutrally Principle and Backbonding

How the complex compound formed?

So what the consequences to the complex compound due to the way

it form?
The more ligand bind, the more negative central atom charge !
 Structure and Bonding
• CO is an unsaturated ligand, by virtue of the C=O multiple bond.
• CO is classed as a soft ligand because it is capable of accepting metal
electrons by back bonding.

This contrasts to hard ligands, which are o donors, and often n donors, too.
• In the CO molecule both the C and
the O atoms are sp hybridized.
This leaves the C py orbital empty, and the O py orbital doubly occupied,
and so the second n bond is formed only after we have formed a dative
bond by transfer of the lone pair of O py electrons into the empty C py
orbital.

• This transfer leads to a C5--O5+ polarization

5+
of5-the molecule, which is
almost exactly canceled out by a partial C -O polarization of all
three bonding
•
orbitals because of the higher electronegativity of
oxygen.
• The free CO molecule therefore has a net dipole moment very close
to zero.
• The metal eg orbital forms a a bond with HOMO orbital of CO.
• The HOMO is a a orbital based on C (due to the higher
electronegativity of O its
orbitals have lower energy).
• The metal t2g orbitals form a n bond with the CO n* LUMO (again
polarized toward C)
• The metal HOMO, the filled M dn orbital, back donates to the CO LUMO
increasing electron density at both C and O because CO n* has both C
and O character. •

• The result is that C becomes more positive

on coordination, and O becomes more
negative. This translates into a polarization
of the CO on binding.
Octahedral
Complex
Molecular orbital diagram
of octahedral complex
involved interaction of both
electrostatic and covalent
interactions
orbitals of the ligand
before the interaction
with the orbitals of the
metal atom
(ligand group orbitals)

orbitals of metal atoms

or metal ions in free
state or before any
interaction with ligands

orbitals of metal atoms

or metal ions in
octahedral complex if
the interaction between
the central atom with
ligands only electrostatic
interactions
molecular orbitalof
octahedral complex
involved interaction
both electrostatic and
covalent interactions
[Co(NH3)6]3+

Central Atom : Co3+

Co3+ : [Ar] 3d6
Ligand : NH3

[Co(NH3)6]3+ is a complex with a strong field, so 10Dq > P

[Co(NH3)6]3+ is diamagnetic, shown with all the pairs of

electrons contained in the complex molecular orbitals.
[CoF6]3+

Central Atom : Co3+

Co3+ : [Ar] 3d6
Ligand : F-

[CoF6]3+ is a complex with a weak field, so 10Dq < P

[CoF6]3+ is paramagnetic, because there are unpaired electrons

in the complex molecular orbitals.
OCTAHEDRAL

– Example 3 Central atom is Fe3+

[FeF6]

The numbers of electron Electron configuration is

donated F- is 17 [Ar} 3d5
OCTAHEDRAL
Example 3

second, fill out

three electrons in
the orbital t2g and
two electrons in
the orbital eg

First, fill out six

pairs of electrons
in the orbital a1g ,
t1u and eg
OCTAHEDRAL

– Example 4 Central atom is Fe3+

[Fe(CN)6]

The numbers of electron Elctron configuration is

donated CN- is 17 [Ar} 3d5
 OCTAHEDRAL
Example 4

second, fill out five

electrons in the
orbital t2g
First, fill out six
pairs of electrons
in the orbital a1g ,
t1u and eg
Tetrahedral
Complex
 VS

MOLECULAR COMPLEX MOLECULAR

ORBITAL DIAGRAM ORBITAL DIAGRAM
TETRAHEDRAL TETRAHEDRAL
COMPLEX MOLECULAR ORBITAL
DIAGRAM
[NiCl4]2-
COMPLEX MOLECULAR ORBITAL
DIAGRAM [FeCl4]2-
Square Planar
Complex
Square Planar

Square planar coordination can be imaginated to results when

two ligands on the z-axis of an octahedron are removed from
the complex, leaving only the ligan in x-y plane. As the z-
ligands move away, the ligands in the square plane move little
closer to the metal.
The orbital splitting diagram for square planar coordination can thus be
derived from octahedral diagram. The splitting diagram for square planar
complexes is more complex than for octahedral and tetrahedral
complexes, and is shown below with the relative energies of each orbital.
Square planar complexes are quite common for the d8 metals in
the 4th and 5th periods: Rh(I), IR(I), Pt(II), Pd(II), and Au(III).
Ni(II) generally forms tetrahedral complexes. Only with very
strong ligands such as CN- , is square planar geometry seen
with Ni(II).