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*2p
O2
2p
2p
2p
larger E
*2s
2s
2s
2s
O
O2
-----------------------------------------------------------------------------------------------------------------*2p
N2
Diamagnetic
Bond order of 3 (NN)
*2p
2p
2p
2p
smaller E
2p
*2s
2s
2s
2s
N
N2
MO Diagram for CO
*2p
LUMO
*2p
2p
2p
2p
2p
2s
*2s
2s
2s
C
CO
- CO is isoelectronic with N2 (C has one less electron than N, O has one more) MO diagram is
very similar to that of N2.
- Diamagnetic, Bond order of 3 (CO)
- Important: HOMO = 2p (weakly antibonding), LUMO = *2p (strongly antibonding)
- Since O is far more electronegative than C, would expect a large dipole moment with - on O.
However, CO actually has only a small dipole moment (0.1 Debye) with the - on Carbon!
Usually electronegativities are a good indication of the direction and magnitude of the dipole on
a molecule, but especially in molecules where orbitals with antibonding character are occupied,
things are not so straightforward.
-----------------------------------------------------------------------------------------------------------------Ordering of MOs in O2 is 2p, 2p, *2p, *2p but in N2 and CO, the order is 2p, 2p, *2p, *2p
Reason - O2 - larger E between s and p orbitals less orbital mixing
- larger E because across the period (B,C,N,O,F) more protons added to the
nucleus, which pulls the electrons in closer to the nucleus (lower energy). This
effect is felt more strongly by the s-orbitals than the p-orbitals, so the energy of
the s-orbitals drops more rapidly than that of the p-orbitals.
- N2 and CO - mixing between the 2p and the *2s orbitals raises the energy of the 2p
above the 2p.
Very wrong theory (for transition metal organometallic chemistry), but quite useful.
Easy way to roughly predict the ordering of the energy levels for a TM compound.
Ligand lone pair thought of as a point charge (e.g. for Cl-, H- or CN-) or the partial negative
charge of a dipole (e.g. for :OH2, :NH3 or :PF3).
Ligands attracted to the TM cation since they are point charges purely electrostatic
bonding assumed.
Any interactions between the electrons of the ligand and those of the metal are repulsive
no covalent bonding (, or ) exists according to this theory!!!
dz2, dx2-y2
axial, eg
o
TM
d-orbitals
inter-axial, t2g
dxz, dyz, dxy
The axial orbitals (eg symmetry in an octahedral environment) point directly towards the
ligands so according to crystal field theory, are raised in energy (unfavourable interaction
between the electrons of the ligands and those of the metal)
The inter-axial orbitals (t2g symmetry in an octahedral environment) do not point directly
towards the ligands, so are lower in energy than the axial orbitals.
dz2, dx2-y2
dx2-y2
large E
dz2
dxy
dz2
dxy
TM
d-orbitals
dxz, dyz
dxz, dyz
octahedral
square pyramidal
square planar
From the octahedral crystal field splitting diagram, pull off one of the ligands along the
z-axis.
Removing the other ligand on the z-axis has the same effect, leading to the energy level
diagram for a square planar complex. Note the large energy gap between the dxy and dx2-y2
orbitals. As a result, square planar complexes are almost exclusively those of d8 metals (all
metal orbitals are filled except the dx2-y2) and so have 16 electrons rather than 18. See later.
Crystal field theory is therefore quite useful for quickly predicting the order of the energy
levels in transition metal complexes. However, the assumption that all bonding is ionic and
no covalent interactions occur is unrealistic. According to this assumption, CO (an excellent
ligand for reasonably electron rich metals) would be predicted to be a terrible ligand (no
negative charge and v. small dipole), ligands would not be expected to bond to metals that do
not have a formal positive charge (i.e. Pd(PPh3)4 and Fe(CO)42- would definitely not exist),
ligands cannot be -donors, -donors or -acceptors, and it is therefore impossible to assess
why o varies with the ligands as it does.
OCTAHEDRAL
TETRAHEDRAL
t2
d orbitals
t ~ 4/9 o
e
M
[ML4]
The same type of approach can be extended in order to figure out the splitting pattern of the
d-orbitals for a variety of other common geometries. Starting from octahedral, one can derive
Jahn-Teller distorted octahedral geometry, square pyramidal and square planar geometry.
By placing the ligands either in the 8 corners or on the 12 edges of a cube, one can derive the
crystal field splitting diagram for 8-coordinate cubic or 12-coordinate cube-octahedral geometry
(similar approach to that used for tetrahedral geometry). The splitting pattern for trigonal planar
geometry can be derived by considering which orbitals or groups of orbitals point most directly
towards the ligands. A similar approach can be used for trigonal bipyramidal geometry, although
the actual ordering of the orbitals is more difficult to rationalise using such simple arguments.
In an octahedral environment, the metal orbitals (3d, 4s, 4p for a 1st row TM) divide by
symmetry into 4 sets: s = a1g, p = t1u, axial d = eg, inter-axial d = t2g.
The orbitals of the six ligands can be combined to give six symmetry-adapted linear
combinations which are of the correct symmetry to interact with the s, 3 x p and 2 x axial-d
orbitals, but not the inter-axial d orbitals.
The result is that 3 orbitals (the inter-axial d-orbitals) are non-bonding, while the rest (6 metal
orbitals and 6 ligand orbitals) combine to form six bonding and six anti-bonding MOs. See
next page.
This is a much more correct approach than crystal field theory, but is not as easy to use.
4p (t1u)
a1g*
4s (a1g)
eg*
O
3d (eg + t2g)
t2g
TM
6L
t1u
a1g
The six bonding orbitals are filled with 12 electrons from the six ligands
Orbitals shown in red (t2g and eg*) are the frontier orbitals where d-electrons reside.
-bonding ligands
(the above MO diagram does not take into account -bonding)
filled orbital
empty orbital
-donor
-donor
-acceptor
NH3, CH3-, H-
For -acceptor ligands, the bonding is SYNERGIC: -donation to the metal strengthens
-backbonding to the ligand, and -donation from the metal to the ligand strengthens the
-donor component of bonding.
This is because -donation leads to increased electron density on the metal, which allows
increased -backdonation. Conversely, -backdonation reduces the amount of electron
density on the metal, which allows more -donation from the ligand to the metal.
-interaction
O
M
slightly antibonding
HOMO of CO
axial d-orbitals
strongly antibonding
* orbitals of CO
Note: The 12 empty *-orbitals of the six CO ligands in a molecule like [Cr(CO)6] can be
combined to form 12 linear combinations of orbitals (3 x T1u, 3 x T2g, 3 x T1g, 3 x T2u). Only the
three linear combinations with T2g symmetry are of the correct symmetry to interact with the t2g
orbitals (dxy, dxz and dyz) on the metal.
4p (t1u)
a1g*
4s (a1g)
t2g*
* orbitals of CO (t2g)
eg*
large
O
3d (eg + t2g)
t2g
(a1g + t1u + eg)
eg
Cr
6 CO
t1u
a1g
-backdonation to CO from the t2g orbitals (which are non-bonding in the absence of
-interactions between the metal and the ligands).
The 3 t2g orbitals and 3 high lying * orbitals of the CO ligands form 3 bonding MOs and
3 antibonding MOs.
Since the CO * orbitals are empty, the d-electrons occupy the bonding MO from this
interaction.
The result is (1) a very large o, so the eg orbital is likely to remain empty.
(2) the t2g orbital is strongly bonding (wants to be filled with 6 electrons)
complexes of strong -acceptor ligands are the most likely to obey the 18 electron rule
* (t2g)
eg*
eg*
L
large
O
-acceptor ligands
increase O
t2g
TM complex with
-bonding only
t2g
[Cr(CO)6]
with -backdonation
from Cr to CO
eg*
-donor ligands
decrease O
eg*
small
O
t2g*
t2g
TM complex with
-bonding only
t2g
-donor ligands
-donation from the ligands to the t2g orbitals the 3 t2g metal orbitals and 3 low lying, filled
ligand orbitals of -symmetry form 3 bonding MOs and 3 antibonding MOs.
Since the interacting ligand orbitals are full, these electrons occupy the bonding MO from this
interaction, and the d-electrons occupy the antibonding MO.
IClNH3
2
2
3
Colour of
the
complex
Purple
Pink
Yellow
eg
Colour
absorbed
Yellow
Green
Blue
o
d
t2g
The colour of the complexes above results from promotion of an electron from the t2g orbital
to the eg orbital. The energy of light absorbed therefore corresponds to the size of o.
[Note: this type of simple treatment can only be applied in certain cases (e.g. d1 or d9
complexes and octahedral 3d complexes with a d4 or d6 configuration). For other
configurations, it is necessary to consult a Tanabe-Sugano diagram and apply a more rigorous
treatment].
For complexes with a single absorption in the visible region of the spectrum, the colour of
light absorbed can be determined from the colour wheel (the colour of the light absorbed is
found opposite the colour of the complex)
Since the order of energy is blue > green > yellow, then the NH3 complex can be seen to have
a larger o than the Cl- complex, which has a larger o than the I- complex.
Since the effect of the ligands on the size of o is a visible change, the resulting series of ligands
is called the spectrochemical series. The order of ligands in the spectrochemical series follows
their behaviour as -donors, -donors or -acceptors very nicely. For o:
I- < Br- < S2- < SCN- < Cl- < F- < OH- < OH2 < MeCN < NH3 < PR3 < CN- < CO < NO+
good -donors
OK -donors
-donors
good -acceptors
However, these -affects are not the whole story, because organometallic ligands such as CH3or H- are located high in the spectrochemical series (H- is similar to CO). Both H- and CH3(in the absence of -agostic interactions) are purely -donor ligands, so their ability to act as high
field ligands is a result of their extremely high -donor ability.