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Ferrocene MO

The document discusses the electronic structure of ferrocene. It describes how the orbitals of the cyclopentadienyl rings interact with the iron orbitals to form molecular orbitals. The document outlines the symmetries of the ligand and metal orbitals and how they combine to give bonding and antibonding molecular orbitals of ferrocene.

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Dmanash Sarmah
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450 views8 pages

Ferrocene MO

The document discusses the electronic structure of ferrocene. It describes how the orbitals of the cyclopentadienyl rings interact with the iron orbitals to form molecular orbitals. The document outlines the symmetries of the ligand and metal orbitals and how they combine to give bonding and antibonding molecular orbitals of ferrocene.

Uploaded by

Dmanash Sarmah
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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The Electronic Structure of Ferrocene

• The two cyclopentadienyl (Cp) rings of ferrocene may be orientated in the two extremes of
either an eclipsed (D5h) or staggered (D5d) conformation.
• The energy of rotation about the Fe Cp axis is very small (~ 4 kJmol 1) and ground state
structures of ferrocene may show either of these conformations.
• There is also very little difference in electronic states between the D5h and D5d symmetries
however the D5d point group representations are used here in the description of the
electronic structure of ferrocene as they simplify the symmetry matching of ligand molecular
orbitals and metal atomic orbitals.
• The primary
Th i orbital
bit l interactions
i t ti th t form
that f th metal
the t l ligand
li d bonds
b d in
i ferrocene
f occur between
b t
the Fe orbitals and the orbitals of the Cp ligand.
• If D5d symmetry is assumed, so that there is a centre of symmetry in the ferrocene molecule
through the Fe atom there will be centro symmetric (g) and anti symmetric (u) combinations.
• The five p orbitals on the planar Cp ring (D5h symmetry) can be combined to produce five
molecular orbitals.
En
nergy
The molecular orbitals of the cyclopentadienyl ring (D5h)
• One combination has the full symmetry of the ring (a2)

• There are two doubly degenerate combinations (e1 and e2) having one and two planar nodes at
right angles to the plane of the ring.

• The relative energies of these orbitals increase as the number of nodes increases.

• The a2 and e1 orbitals are both fully occupied in the electronic configuration of the Cp anion
whereas the e2 orbitals are net anti bonding and are unfilled.

• For a bis cyclopentadienyl metal complex ( 5 Cp)2M , such as ferrocene, the orbitals of the two
Cp ligands are combined pairwise to form the symmetry adapted linear combination of
molecular orbitals (SALC’s).
• To do this, the sum and difference of corresponding
p g molecular orbitals on the Cp
p ligand
g

must be taken, e.g. ( 1+ 1), ( 1 1); ( 2+ 2), ( 2 2) etc.

• F example,
For l ' 1+ 1' gives
i rise
i tot a molecular
l l orbital
bit l off a1g symmetry.
t

• Overall, this gives rise to three sets of ligand molecular orbitals of gerade (g) and ungerade

(u) symmetry with respect to the centre of inversion;

a low lying filled bonding pair of a1g and a2u symmetry

a filled weakly bonding pair of e1g and e1u symmetry

an unfilled anti bonding pair of e2g and e2u symmetry.


SALC’s for a ( 5 Cp)2M complex; = A1g + A2u + E1g + E1u + E2g + E2u

e2g e2u

e1gg e1u

Y
X

a1g a2u
• The metal orbitals transform as

A1g (dz2, s) + A2u (pz) + E1u (px, py) + E1g (dyz, dxz) + E2g (dx2 dy2, dxy)

• reducible representation of SALC’s :

= A1g + A2u + E1g + E1u + E2g + E2u

• Byy consideringg these ligand


g molecular orbitals and how overlap
p with metal atomic orbitals can
be affected the molecular orbital bonding picture of ferrocene can be constructed.
• For example, the a1g SALC orbital can in theory overlap with the Fe 4s and 3dz2 orbitals as they
are also of a1g symmetry. This interaction gives rise to the bonding and anti bonding
molecular
l l orbitals
bi l off the
h complexl a1g and d a1g* respectively.
i l
• Each combination of ligand molecular orbitals and metal molecular orbitals leads to a bonding
molecular orbital [( ligand molecular orbital)+( metal atomic orbital)] and a corresponding anti bonding
molecular orbital [( ligand
li d molecular bi l) ( metall atomic
l l orbital bi l)] providing that the energies of the
i orbital
two component sets are sufficiently close for overlap.
Symmetry matching of the SALC’s with the metal atomic orbitals

no metal no metal
orbital of orbital of
appropriate appropriate
symmetry symmetry
dxy dx2-dy2 available available

e2g e2u

dyz dxz py px

e1gg e1u

Y
X
s dz2 pz

a1g a1u
A qualitative molecular orbital diagram for ferrocene (D5d)

pz py px
a1u e1u

dyz dxz
e1g

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