 Molecular Orbital Theory – Octahedral, Tetrahedral or Square Planar

Complexes
The crystal field theory fails to explain many physical properties of the transition metal complexes
because it does not consider the interaction between the metal and ligand orbitals. The molecular orbital theory
can be very well applied to transition metal complexes to rationalize the covalent as well as the ionic character
in the metal-ligand bond. A transition metal ion has nine valence atomic orbitals which are consisted of five
nd, three (n+1)p, and one (n+1)s orbitals. These orbitals are of appropriate energy to form bonding interaction
with ligands. The molecular orbital theory is highly dependent on the geometry of the complex and can
successfully be used for describing octahedral complexes, tetrahedral and square-planar complexes. The main
features of molecular orbital theory for metal complexes are as follows:
1. The atomic orbital of the metal center and of surrounding ligands combine to form new orbitals, known as
molecular orbitals.
2. The number of molecular orbitals formed is the same as that of the number of atomic orbitals combined.
3. The additive overlap results in the bonding molecular orbital while the subtractive overlap results in the
antibonding overlap.
4. The energy of bonding molecular orbitals is lower than their nonbonding counterparts while the energy of
antibonding molecular orbitals is higher than that of nonbonding orbitals.
5. The energy of nonbonding orbitals remains the same.
6. The ionic character of the covalent bond arises from the difference in the energy of combining orbitals.
7. If the energy of a molecular orbital is comparable to an atomic orbital, it will not be very much different in
nature from atomic orbital.
The polarity of the bond can be explained by considering the overlap of two atomic orbitals of
different energies. Suppose ϕA and ϕB are two atomic orbitals of atoms A and B, respectively. These two atomic
orbitals have one electron in each of them and combine to form one bonding (σ) and one antibonding (σ*)
molecular orbital. After the formation of molecular orbitals, both electrons occupy σ-orbital. Now, if the energy
of σ-orbital is closer to ϕA, it will have more ϕA character and hence the electron density of both of the electrons
will be concentrated more on atom A than B. Similarly if the energy of σ-orbital is closer to ϕB, it will have
more ϕB character and the electron density of both of the electrons will be concentrated more on atom B than
A. This same explanation holds for the ionic character in metal-ligand bond.
The main concern here is that the total number of the molecular orbitals formed as a result of bonding
and antibonding interactions is quite large; and therefore, many complications related to the understanding of
symmetry-energy may arise, all of which needs a very sophisticated treatment of chemical bonding. Hence,
without a comprehensive knowledge of the chemical applications of group theory, it is quite difficult to explain
the whole concept. However, a primitive explanation for the σ-bonding in transition metal complexes of
different geometry can still be given.
  Octahedral Complexes
In octahedral complexes, the molecular orbitals created by the coordination of metal center can be
seen as resulting from the donation of two electrons by each of six σ-donor ligands to the d-orbitals on the
metal. The metal orbitals taking part in this type of bonding are nd, (n+1)p and (n+1)s. It should be noted down
that not all nd-orbitals but only dz2 and dx2−y2 orbitals are capable of participating in the σ-overlap. The dxy, dxz
and dyz orbitals remain non-bonding orbitals. The ligands approach the metal center along the x, y and z-axes
in such a way that their σ-symmetry orbitals form bonding and anti-bonding combinations with metal’s s, px,
py, pz, dz2 and dx2−y2 orbitals. A total of six bonding and six anti-bonding molecular orbitals formed. The
symmetry designations of different metal orbitals taking part in octahedral overlap are:

dz2, dx2−y2 – eg

s – a1g

px, py, pz – t1u

dxy, dxz, dyz – t2g

The exact nature of the Mulliken symbols, like eg or a1g, etc., can be understood only after the core
level understanding of group theory. However, it still can be noted that a, e and t represents singly, doubly and
triply degenerate orbitals, respectively. The subscripts g and u represent gerade and ungerade nature of the
orbitals. An orbital is said to be gerade if it has the same sign in all opposite directions from the center. These
are also said to be having the centre of symmetry. On the other hand, an orbital is said to be ungerade if it has
the opposite sign in all the opposite directions from the center. These are also said to be lacking the centre of
symmetry.
The symmetry adapted linear combinations of atomic orbitals (SALCs) for metal-ligand direct
overlap can be obtained just by resolving the reducible representation based on the bond vectors along the axis
of σ-overlap. As there are total six bond vectors for the metal-ligand σ-bonding, hexa-dimensional reducible
representation will be obtained. As the six ligands in an octahedral complex approach the central metal ion
along the three Cartesian axes (two along x-axis, two along y-axis and two along z-axis), the six σ-basis bond
vectors must also be selected along x, y and z-axis.

Figure 3. Continued on the next page…

 Figure 3. The octahedral coordination and corresponding σ-basis set for ligand orbitals in octahedral
complexes.

The symmetry adapted linear combinations of these fall into three irreducible representations labeled as a1g,
eg, and t1u. The symmetry designations of different ligand orbitals taking part in octahedral overlap are:

Table 1. Reducible representation based on bond vectors in the octahedral geometry.

Oh E 8C3 6C2 6C4 3C2 i 6S4 8S6 3σh 6σd Irreducible

components

Γπ 6 0 0 2 2 0 0 0 4 2 a1g + eg + t1u

The metal-orbital sets of a1g, eg and t1u symmetry participate in σ-bonding by interacting with the
same symmetry SALCs sets to produce σ-bonding and antibonding molecular orbitals. However, the triply
degenerate t2g orbitals set on the metal remains nonbonding as there no ligand orbitals of this symmetry. The
exact nature of the “symmetry adapted linear combination of atomic orbitals” or simply SALCs is quite
complex and is beyond the scope of this volume but still we can simply give a superficial explanation for these
ligand orbitals. The pictorial representation of various SALC orbitals in octahedral complexes, capable of σ-
overlap with metal orbitals, can be given as:
1. If the six atomic orbitals of six ligands are pointing their positive lobes towards metal’s s-orbital, then the
composite orbital becomes:

φ1 = σ1 + σ2 + σ3 + σ4 + σ5 + σ6 (1)

The pictorial representation is given below.

 Figure 4. The combination of ligand orbitals overlapping with s-orbital of the metal center.

2. The px-orbital of metal center can overlap with ligands atomic orbital approaching along the x-axis. Hence,
the composite orbital becomes:

φ2 = σ1 – σ2 (2)

The pictorial representation is given below.

Figure 5. The combination of ligand orbitals overlapping with px-orbital of the metal center.
3. The py-orbital of metal center can overlap with ligands atomic orbital approaching along y-axis. Hence, the
composite orbital becomes:

φ3 = σ3 – σ4 (3)

The pictorial representation is given below.

Figure 6. The combination of ligand orbitals overlapping with py-orbital of the metal center.

4. The pz-orbital of metal center can overlap with ligands atomic orbital approaching along z-axis. Hence, the
composite orbital becomes:

φ4 = σ5 – σ6 (4)

The pictorial representation is given below.

Figure 7. The combination of ligand orbitals overlapping with pz-orbital of the metal center.
5. The dx2–y2 orbital of metal center can overlap with ligands atomic orbital approaching along x and y-axis.
Hence, the composite orbital becomes:

φ5 = σ1 + σ2 – σ3 – σ4 (5)

The pictorial representation is given below.

Figure 8. The combination of ligand orbitals overlapping with dx2–y2 orbital of the metal center.

6. The dz2 orbital of metal center can overlap with ligands atomic orbital approaching along x, y and z-axis.
Hence, the composite orbital becomes:

φ6 = σ5 + σ6 – σ1 – σ2 – σ3 – σ4 (6)

The pictorial representation is given below.

Figure 9. The combination of ligand orbitals overlapping with dz2 orbital of the metal center.
The overall molecular orbital energy level diagram for σ-bonding in octahedral complexes can be shown as:

Figure 10. The formation of σ-molecular orbitals (bonding, antibonding and non-bonding) in octahedral
complexes of transition metals.
 The φ1 composite orbital of a1g symmetry interacts with a1g orbital set of metal ions and produces one
bonding (a1g) and one antibonding molecular orbital (a*1g). The φ2, φ3 and φ4 composite orbital set of t1u
symmetry interacts with t1u orbital set of metal ions and produces triply-degenerate bonding (t1u) and triply-
degenerate antibonding molecular orbital (t*1u) set. The φ5 and φ6 composite orbital set of eg symmetry interacts
with eg orbital set of metal ions and produces doubly-degenerate bonding (eg) and doubly-degenerate
antibonding molecular orbital (e*g) set. The t2g orbital set of the metal center remains non-bonding in nature.
The electron-filling in various orbitals is done in accordance with the Aufbau principle, Hund’s rule and Pauli
exclusion principle.
Some typical explanations in the view of MO-theory are:
i) Spin only magnetic moments: Just like crystal field theory, MO-theory can also be used to rationalize the
spin only magnetic moments of different transition metal complexes. For instance, 5.9 B.M. magnetic moment
of [Mn(H2O)6]2+ is generated when seventeen electrons (five from Mn2+ and twelve electrons from six aquo
ligands) are filled in different molecular orbitals. Twelve out of seventeen electrons occupy six bonding
molecular orbitals of a1g, t1u and eg. Three out of the remaining five electrons are filled in nonbonding t2g and
the last two electrons occupy e*g giving a total of five unpaired electrons.
ii) 18- electron rule: It is a well-known fact that metal carbonyls and many other complexes follow 18-electron
rule quite well. This is also analyzed in terms of effective atomic number which suggests that a total of 18-
electrons in the valence shell generally makes overall electron-count to resemble a noble gas core. However,
a strong basis for this rule can found in molecular orbital theory. Six bonding molecular orbitals can
accommodate a total of 12 electrons and only six electrons can be filled in the non-bonding t2g. Any extra
electron is bound to occupy the antibonding e*g orbital and hence affects the stability.
iii) The splitting of d-orbital: According to crystal field theory, the splitting, Δo of d-orbital in t2g and eg is
produced by the difference in the Coulombic repulsion experienced various metal orbitals. However, the
molecular orbital theory sees the splitting of d-orbital as a result of the interaction of metal orbitals with ligand
orbitals and labels it as splitting between nonbonding t2g and antibonding e*g.
iv) High spin – low spin complexes: Just like in the case of crystal field theory, the magnitude of Δo decides
the multiplicity nature of the complexes. If the separation between nonbonding t2g and antibonding e*g is pretty
large, the electrons prefer to pair up with the electrons already present in nonbonding t2g and the complex
becomes low-spin. On the other side, If the separation between nonbonding t2g and antibonding e*g is small,
the electrons prefer to occupy antibonding e*g and the complex becomes high-spin. For example, in
[Co(NH3)6]3+, the magnitude of Δo is very large and the configuration becomes t2g6, e*g0. Furthermore, the
comparatively lower stability and weaker metal-ligand bond in high spin complexes may be attributed to the
presence of electrons in a molecular orbital of antibonding nature.
v) Jahn-Teller distortions: The concept of molecular orbital theory can also be used to rationalize the z-out
or z-in distortion of the octahedral metal complexes. For example, octahedral complexes of Cu2+ ion have been
known to undergo Jahn-Teller distortion due to d9 configuration. According to molecular orbital theory, the
electronic configuration octahedral complexes of Cu2+ will be t2g6, e*g3. Now, as the energy of eg* molecular
 orbital is close to the pure atomic orbitals of metal ion, eg* would resemble more to the metal orbitals than the
ligand’s. Therefore, we can approximate eg* to pure dx2–y2 and dz2. Now if the configuration is (dx2–y2)1 (dz2)2,
higher antibonding electron density along z-axis would result in a weaker bond and an elongation of bonds
would take place along z-axis, giving a z-out distortion. On the other hand, if the configuration is (dx2–y2)2 (dz2)1,
higher antibonding electron density along x and y-axis would result in a weaker bond and an elongation would
take place along x and y-axis, giving a z-in distortion.
vi) Variation of ionic radii: Experimental values of ionic radii of central metal ions in bivalent salts of first
transition series were very well explained by the crystal field theory. The same can be done in the frame of
molecular orbital theory. The decrease in ionic radii, when one moves from Ca2+ to V2+, may be attributed to
the increasing magnitude of effective nuclear charge while the filling of valence electrons takes place in
nonbonding t2g. However, after V2+, the fourth electron in Cr2+ is filled in antibonding e* and this effect makes
the metal-ligand bond to increase, which in turn results in an increment in effective ionic radius. This trend
continues up to Mn2+, but as we move from Fe2+ to Ni2+, the electron filling again goes to nonbonding t2g and
thus thereby decreases the ionic radii. The ninth and tenth electron in Cu2+ and Zn2+ are filled in antibonding
e* and therefore, the effective ionic radius increases again. The whole situation creates two minima in effective
ionic radii, one for V2+ and other for Ni2+.
It is worth to note down that the more sophisticated rationalization of the MO-diagram for octahedral
complexes can be given in the terms of molecular symmetry combined with detailed quantum mechanics
involved. In general practice, six symmetry-adapted linear combinations (SALCs) of atomic orbitals,
corresponding to the irreducible components of the bond-vector based reducible representation, are created.
The irreducible representations that these SALCs span to are a1g, t1u and eg. The metal also has six valence
orbitals that span the same irreducible representations (s-orbital is labeled as a1g, a set of three p-orbitals is
labeled t1u, and the dz2 and dx2−y2 orbitals are labeled eg). The six σ-bonding molecular orbitals result from the
combinations of ligand SALC's with metal orbitals of the same symmetry.

RELATIVE ORDER OF ENERGY OF DIFFRENT MOS

For strong σ-bonding , BMOs will be lowered in energy and the corresponding
ABMOs will be raised in energy compared– to the energy of six ligand orbital
combinations. –

–
 complex
octahedral
ligands
the
electron
pairing
non-bonding
orbit- Mo different six (3dy.
orbitals
(HSsmaller
ligands (three)),
orbitals
different
strong is e of 23.12.
orbitals
and
weak energies t,
of to, Fig and3d
non-bonding
are he energy
t, than
greater
is Six ABMOs
X BMOs in ligands aree* of in (two)
between 23.11: Six
o orbitals andenergies
complex
of
shown
order electrons.
of
order tgg) e,
Fig 0r AOs
non-bonding
Three strong to.
different
(one),
(A) tËu) (LS
octahedral
complex) between
the
relative
as three
(rq octahedral
in
relative
shown
orèeg)
G2-2(Ga 3dx, or or
eg) having result
becomes with
[a,,
[ajand
cases. gapABMOs
= (o (o, of
energy (A,) the BMOs
BMOs flling
(three)]
energy -y large
isA, 0, complex complexes
twogiven the as P) 3dyz
(A,> gap
given
a Hence
As
e* result = six for
six
is = o 0, (aj) o, of P). Electrons
a theand complexes
following 3d,yy = = Order
octahedral
energy
a (A,< same. have available
in 3d,) o, x t
then a
present
in
present octahedraland
As 23.11 theP the we
andP). octahedral
the complexes), increases
Energy (two)
of
then almost withthat are
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ligands (A,> Figan ligandsvalue
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als
(3dyP thebecomes
us energy, in 3d)
let the(LS LS Ifthe than MOs 23.7
of [a, ZX
NowIf in Filling and
FigABMOs
(i) (iü)
34,
 725
as:
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whereas in
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andion
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ionbe
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can andnon-bonding
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=2-y2 metalfree d, BMOs+
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oFourABMOs "2
2 e BMOs
Six
o sixthansix of six distribution
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of d-orbitals
ion t,o
weak the in orbitals the
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rather if metal occupy
(Two of o,2 ABMOs,occupy
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six o,2 e, in of willthe
Complexes energy will
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3d,yz AOs) 0, pure e
(BMO^)12 and ligands
o2 = 6 contribution metal
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are previously octahedral
Octahedral = (Three G2= Oy Order
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Ta 23.12 we
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 Selected TopicS in Inorganic
1. Chemistry
(AlsoOctahedral
See Fig. Complexes
23.11)
Having Strong Ligands(LS
Complexes)
In case of LS
cupythe six BMOs octahedral
and the complexes, 12 electrons donated by six ligands will oc-
to tgg electrons present in d-orbitals of the free metal ion will go
extra non-bondingof orbitals until these orbitals are completely filled and if required, the
electrons
in various BMOs, d-orbitals will occupy e ABMOs. Thus the distribution of electrons
non-bonding d-orbitals and e ABMOs of otahedral complexxes of d'
1on (*= l to 10) having strong ligands (LS complexes) can be written as shown below
Obviously total number of electrons in octahedral complex of d ion is equal to
(12 +x ). This number is given in bracket.
d' ion (12 + 1= 13) =(BMOs)
(3d,) n =1,
= (BMOs)? S=n/2=0.5
d ion (12 + 2 = 14) = (BMOs) (3d,) (3d,!
xy n=2,
(BMOs)" (t S=1
ion (12 +3= 15) = (BMOs)2 (3d,) (3d,)' (3d,)' n=3,
= (BMOs)2 3
(tgg S= 1.5
d'ion (12 + 4 = 16) = (BMOs)" (3d,y° (3d,) (8d n=2,
(BMOs)" (tog' S=1
d° ion (12 + 5 = 17) = (BMOs)"
(3d,, (34, (3d,)' n=1,
=(BMOs) (t S=0.5
d° ion (12 + 6= 18) = (BMOs)"
(3d,, (3d, (3d,* n=0,
=(BMOs)" (ta)6 S=0
d' ion (12 +7 = 19) = (BMOs) n=1,
=(BMOs) (t) S= 0.5

ion (12 +8 = 20) =(BMOs)" (3d,y (3d, ) (3d,) (o)(o n=2,

= (BMOs)2 6
(tzg S=1

a ion (12 +9 = 21) =(BMOs)" (3d,y (3d,' (3d, y° (o)( ) n=l,

(BMOs)'2 S= 0.5

d°ion (12 + 10 = 22) = (BMOs) (3d,y (3d, ) (3d,, (o (a n= 0,

=(BMO) (t (e S=0

In case of LS octahedral complexes, the energy difference (A) between no

bonding t2g orbitals (dy dyg and d) and e ABMOs is greater than the electrc
pairing energy, P(A,>P).
Molecl dral Complexes
727
Octahedral
2.
(Also See Fig. 23.12)Complexes Having Weak Ligands ((HS Complexes)
In case of HS
accomdated in six octahedralcomplexes, 12
BMOs. energyelectrons
Now since the donated by six ligands are
orbitals and e ABMOs is
smaller than the difference (A) between non-bonding
non-bonding tg Orbitals and e ABMOs have electron pairing energy, P(A, < P),
the electrons present in d-orbitals of the free
almost the same energy. As a result,
and e
ABMOs in accordance with metal ion occupy t2g non-bonding AOs
Hund's rule, i.e. the pairing of electrons in three
tog non-bonding orbitals and two e ABMOs takes
place only after these five orbit-
als are at least singly filled. Thus the
non-bonding tg orbitals and e ABMOs distribution of
of octahedral electrons in
various BMOs,
10)having weak complexes of d ion (* =1to
ligands (HS complexes) can be written as:
+ l= 13): =
ion (12 (BMOs)"(3d)'
xy n = 1,
= (BMOs) (t S=n/2=0.5
Pion (12 +2 = 14) = (BMOs) (3d,)(3d,)' n =2,
= (BMOs) (t)2 S=1
ion (12 + 3 = l5) = (BMOs)* (3d,)(3d)(3d) n =3,
= (BMOs)? S= 1.5
a ion (12 + 4 = 16) = (BMOs)2 n=4,
= (BMOs)12 S= 2

a' ion (12 +5= 17) =(BMOs) (34,,'(84,'(3d,at (oe n =5.

= (BMOs)l2
(tgg S= 2.5

a ion (12 +6 = 18) =(BMOs) (3d (3d,, (3d,,)'(ß;) (ß) n=4,

= (BMOs)12 S = 2

|a'ion (12 +7= 19) =(BMOs)" (3d, (3d,,y° (3d,, (o)' (o a n=3,
2 S=1.5
(BMOS)" (tg (
d ion (12+ 8= 20) = (BMOs) (3d,'(3d, (3d (o)(d) n=2,
S=1
(BMOs)" (tz)(
d ion (12 +9=21) = (BMOs) (3d°(3d, (3d´(o)» (o) n=1.
S=0.5
= (BMOs) (tgg (et
d ion (12+ 10 =22) =(BMOs) (3d,,j (3d, (3d,) (op) (¡
n =0,

S=0
=(BMOs)P (t) (e)*
= 12+ 1 13)
Sigma (o) Bonding in [Ti (H,0),l Ion (e is a d'ion (-3d'4s'4p9)
present as T* ion which
In (Ti(H,0).j3t ion, Ti is electrons from six H,O ligands and one electror
Ihus the complex ion has 12
  π-Bonding and Molecular Orbital Theory
We have already studied the metal-ligand σ-overlap in the framework of molecular orbitals theory.
Furthermore, this theory is also very useful for providing a rational explanation for the π-bonding in different
metal-complex geometries. The basic approach remains the same except the fact that the orbital overlap in this
situation is not along the internuclear axis but is sidewise in nature. The symmetry criteria governing these
overlaps are absolutely clear but the extant up to which the overlap for different ligands takes place is still a
matter of debate. In other words, the matching of metal and ligands orbital symmetry is not sufficient to assure
the formation of π-bond as there are also some other factors (like size and energy) that signify the extent of
overlap. It is quite possible that two orbital sets with the same symmetry may not be able to form molecular
orbital due to a large difference in their energies.
There are four different types of metal-ligand interaction which can be resulted from the sidewise
overlap of the orbitals.

(a) (b)

(c) (d)

Figure 15. The sidewise overlap (π-bonding) of the d-orbital metal with different types of ligands orbital
(a) dπ-pπ, (b) dπ-dπ, (c) dπ-π*, (d) dπ-σ*.

Electron density can be transferred from filled ligand orbital to the empty d-orbital of the metal center, or from
the filled d-orbital of the metal to the empty orbital of the ligand.
 Table 4. Different types of π-bonding and the compatibility of various ligands.

Type Explanation Examples of the ligands involved

dπ-pπ Transfer of electron density from filled p- RS–, RO–, O2–, F–, Cl–, Br–, I–, R2N–
orbital of the ligand to the empty d-orbital
of the metal.

dπ-dπ Transfer of electron density from filled d- R2S, R3P, R3As

orbital of the metal to the empty d-orbital
of the ligand.

dπ-π* Transfer of electron density from filled d- CN–, CO, RNC, N2, NO2, ethylene,
orbital of the metal to the empty π*-orbital pyridine
of the ligand.

dπ-σ* Transfer of electron density from filled d- R3P, H2, alkanes

orbital of the metal to the empty σ*-orbital
of the ligand.

It can be seen from the above table that some ligands belong to more than one category and hence can use
more than one type orbitals for π-bonding. However, it is observed that the contribution from one type of
orbitals dominates the other in many cases. For instance, R3P can accept d-electron density from metal in its
empty d-orbital, or in the antibonding σ* which is also greater in magnitude. Similarly, I– also has the ability
to donate electron from its filled p-orbital, or to accept electron density in its low lying empty d-orbitals.
The generally accepted explanation for the π-bonding in transition metal complexes of different
geometry can be given as:
 π-Bonding in Octahedral Complexes
The π-bonding in octahedral complexes can happen in two ways; one through ligand p-orbitals that
are not being used in σ bonding and other via π or π* molecular orbitals present on the ligand. The symmetry
designations of different metal orbitals taking part in octahedral overlap are:

dz2, dx2−y2 – eg

s – a1g

px, py, pz – t1u

dxy, dxz, dyz – t2g

The symmetry adapted linear combinations of atomic orbitals (SALCs) for metal-ligand sidewise
overlap can be obtained just by resolving the reducible representation based on the displacement vectors
perpendicular to the axis of σ overlap. As each of the six ligands has two basis-vectors for π-symmetry, there
are twelve in total.

Figure 16. The π-basis set for ligand orbitals in octahedral complexes.

The symmetry adapted linear combinations of these fall into four triply degenerate irreducible representations
labeled as t1g, t2g, t1u and t2u. The symmetry designations of different metal orbitals taking part in octahedral
overlap are:

Table 5. Reducible representation based on perpendicular vectors in the octahedral geometry.

Oh E 8C3 6C2 6C4 3C2 i 6S4 8S6 3σh 6σd Irreducible

components

Γπ 12 0 0 0 –4 0 0 0 0 0 t1g + t2g + t1u + t2u

Two of these aforementioned sets are of t2g and t1u symmetry. The dxy, dxz and dyz orbitals set on the
metal also have t2g symmetry, and therefore the π-bonds formed between a central metal and six ligands also
have it as these π-bonds are just formed by the overlap of two sets of orbitals with t2g symmetry. Similarly, the
px, py and pz-orbital set of the metal has t1u symmetry which resembles with the symmetry of ligands SALCs.
Therefore, these same-symmetry (t1u) sets from metal and ligand may also interact to create bonding and
antibonding molecular orbitals. However, the participation of t1u set of the metal in π-overlap is highly disliked
because the orbitals corresponding to this set are already being used in stronger σ-bonding and any deviation
from this state is bound to destabilize the complex.
Hence, the SALC sets of t1g, t2u and also t1u remain nonbonding. The pictorial representation of
different SALC-orbitals in octahedral complexes, capable of π-overlap with metal orbitals, can be given as:
1. If four perpendicular p-orbitals of four ligands approaching along x and y-axis are pointing their lobes
towards metal’s dxy-orbital in a sidewise manner, then the composite orbital becomes:
 φ1 = π1 – π2 + π3 – π4 (7)

The pictorial representation is given below.

Figure 17. The combination of ligand orbitals overlapping with dxy-orbital of the metal centre.

2. If four perpendicular p-orbitals of four ligands approaching along y and z-axis and are pointing their lobes
towards metal’s dyz-orbital in a sidewise manner, then the composite orbital becomes:

φ2 = π3 – π4 + π5 – π6 (8)

The pictorial representation is given below.

Figure 18. The combination of ligand orbitals overlapping with dyz-orbital of the metal center.

3. If four perpendicular p-orbitals of four ligands approaching along x and z-axis are pointing their lobes
towards metal’s dxz-orbital in a sidewise manner, then the composite orbital becomes:
 φ3 = π1 – π2 + π5 – π6 (9)

The pictorial representation is given below.

Figure 19. The combination of ligand orbitals overlapping with dxz-orbital of the metal center.

Molecular orbitals and the effect of π-bonding on crystal field splitting can be categorized in three ways as
follows:
1. When ligand π-orbitals are filled and are of lower energy: The one form of coordinative π-bonding is
ligand-to-metal bonding. This situation arises when the t2g-symmetry p or π-orbitals on the ligands are filled
and are low in energy. They combine with the dxy, dxz and dyz orbitals on the metal and donate electrons to the
resulting π-symmetry bonding orbital between them and the metal.
The metal-ligand bond is somewhat strengthened by this interaction, but the complementary anti-
bonding molecular orbital from metal-ligand overlap is not higher in energy than the antibonding molecular
orbital from the σ-bonding. The molecular orbital of t2g* are greater in energy than nonbonding sets of t1g, t2u
and t1u. On the other hand, the bonding molecular orbitals of t2g are lower in energy than that of nonbonding
SALCs of the ligands.
Therefore, when 36 electrons (12×2 from π-bonding and 6×2 from σ-bonding) from ligands are filled
in the molecular orbitals, they will completely saturate the a1g-bonding, t1u-bonding, eg-bonding, t2g-bonding
and the nonbonding sets of t1g, t2u and t1u. The electron previously filled in d-orbital of the free metal ion can
now be considered as distributed between t2g* and eg*. Hence, the crystal field splitting Δo decreases when
ligand to metal bonding takes place.
The overall molecular orbital energy level diagram for this type of π-bonding in octahedral complexes
can be shown as:
 Figure 20. The generation of π and σ-molecular orbitals in octahedral complexes.

2. When ligand π-orbitals are empty and are of higher energy: The second important form of π-bonding in
coordination complexes is metal-to-ligand π bonding, also called π-backbonding. It occurs when the LUMOs
(lowest unoccupied molecular orbitals) of the ligand are anti-bonding π*-orbitals and are high in energy. The
ligands end up with electrons in their π* molecular orbital, so the corresponding π-bond within the ligand
weakens. The complementary anti-bonding molecular orbital from metal-ligand overlap is higher in energy
than both, the first antibonding molecular orbital from the σ-bonding (eg*), and the nonbonding sets of t1g, t2u
and t1u. On the other hand, the bonding molecular orbitals of t2g are higher in energy than all σ bonding
molecular orbitals. The overall molecular orbital energy level diagram for this type of π-bonding in octahedral
complexes can be shown as:

Figure 21. The generation of π and σ-molecular orbitals in octahedral complexes.

 Therefore, when twelve electrons (12×0 from π-bonding and 6×2 from σ-bonding) from ligands are
filled in the molecular orbitals, they will completely saturate the a1g-bonding, t1u-bonding and eg-bonding. The
electron previously filled in d-orbital of the free metal ion can now be considered as distributed between t2g
and eg*. Hence, the crystal field splitting Δo increases and the bond between the ligand and the metal strengthens
when metal to ligand bonding takes place.
3. When ligand π-orbitals are empty as well as filled: There are many ligands, like I–, which have both filled
p-orbitals as well as vacant d-orbitals of π symmetry. In these cases, the prediction of crystal field splitting
energy is quite difficult as the two effects counterbalance each other to different extents for different ligands.
The six bonding MOs which are formed are actually filled by the electrons coming from the ligands, and
electrons from the d-orbitals of the metal ion occupy the nonbonding and, sometimes, antibonding molecular
orbitals. The energy difference between the latter two types of MOs is called Δo and is determined by the nature
of the π-interaction between the ligand orbitals with the d-orbitals on the central atom. As described above, π-
donor ligands lead to a small Δo and are called weak- or low-field ligands, whereas π-acceptor ligands lead to
a large value of Δo and are called strong or high-field ligands. Ligands that are neither π-donor nor π-acceptor
give a value of Δo somewhere in-between.
The magnitude of Δo determines the electronic structure of d4-d7 metal ions., The nonbonding and
antibonding MOs in types of metals complexes can be filled in two ways; the first one in which maximum
possible electrons are put in the nonbonding orbitals before the antibonding filling, and second one in which
maximum possible unpaired electrons are put in. The first case is labeled as low-spin, while the second is
labeled as high-spin complexes. A small Δo can be outranked by the energetic stabilization from avoiding the
electron pairing, leading to the spin-free case. On the other hand, if Δo is large, the spin-pairing energy would
become negligible in comparison and a spin-paired state arises. An empirically-obtained list of various ligands
which are arranged by the magnitude of splitting Δ they produce is called as the spectrochemical series. It can
be seen that the low-field ligands are all π-donors (such as I−), the high field ligands are π-acceptors (such as
CN− and CO), and ligands such as H2O and NH3, which are neither, are in the middle.
I– < Br– < S2– < SCN– < Cl– < NO3– < N3– < F– < OH– < C2O42– < H2O < NCS– < CH3CN <
py (pyridine) < NH3 < en (ethylenediamine) < bipy (2,2'-bipyridine) < phen (1,10-phenanthroline) < NO2– <
PPh3 < CN– < CO
It is also worthy to note that the electrons transfer from metal d-orbital to the antibonding molecular
orbitals of carbonyl and its analogs is actually partial in nature. The electron-transfer increases metal-carbon
bond strength but weakens the carbon–oxygen bond. The increased M–CO bond strength is obvious in the
increases of vibrational frequencies for the metal–carbon bond and usually lie outside the range of normal IR
spectrophotometers. Moreover, the bond length of M–CO bond is also shortened. The decreased bond strength
of C–O bond is obvious from the decreasing wavenumber of νCO bands. The high stabilization which results
from metal-to-ligand bonding (back-bonding) is caused by the relaxation of the negative charge from the metal
center. This permits the metal ion to accept the σ-donation more effectively. The combination of ligand-to-
metal σ-bonding and metal-to-ligand π-bonding is a synergic effect, as each enhances the other.