Group 3

Molecular Orbital Theory

Ruth Natalia

Dinar Anugrah 1406344

Rizka P.

1401464

Suci A.

1406080

Elsa D.

1405206

Aisyah D.I.

Desi S.

Alliefsa T.

Milantika D.P.

Ruslan F. 1406390

Ari N.F.

1401394

1400931
1406315
1400932

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

Molecular Orbital is
the result of
overlapping and
merging of atomic
orbitals in a
molecule.

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
Antibonding molecular orbitals are
orbitals with electron density away from
the central belt area between the
nucleus together and produce a less
stable situation.
nonbonding orbital molecular orbital
that is what happens when the area
overlaps exist unreacted atomic orbitals
in bonding

Spectrochemical
Series

Spectrochemical series
Aspectrochemical seriesis a list ofligands
ordered on ligand strength and a list of metal ions
based onoxidation 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 partialspectrochemical serieslisting of ligands
from small to large 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

separationd,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 I2. 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 of the

molecule, which is almost exactly canceled out by a partial
C5+-O5- polarization of all three bonding orbitals because of
thefree
higher
electronegativity
ofhas
oxygen.
The
CO molecule
therefore
a net dipole moment very
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

CO
TheLUMO
resultincreasing
is that C becomes
the
electron more
density at both C and O
positive
andOOcharacter.
because
COon
n*coordination,
has both C and
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 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

orbitals of the
ligand before the
interaction with
the orbitals of the
metal atom
(ligand group
orbitals)

molecular orbitalof
octahedral
complex involved
interaction both
electrostatic and
covalent

[Co(NH3)6]
Central Atom

3+

: 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+

[FeF
6
The numbers of
electron donated Fis 17

Electron
configuration is
[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 donated CNis 17

Elctron configuration
is
[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
ORBITAL DIAGRAM
TETRAHEDRAL

COMPLEX
MOLECULAR
ORBITAL DIAGRAM
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 zligands 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 d 8 metals in

the 4th and 5th periods: Rh(I), IR(I), Pt(II), Pd(II), and Au(III).
Square planar complexes are rare for the 3 rd periods metals.
Ni(II) generally forms tetrahedral complexes. Only with very
strong ligands such as CN- , is square planar geometry seen with
Ni(II).