Transition Metal Complexes

Electronic Spectra 2
Electronic Spectra of Transition Metal
Complexes
Cr[(NH
3
)
6
]
3+
d
3
complex
Molecular Term Symbols
Quartet states
Doublet state
Different Ways of
Transitions
a) d
z
2
d
xy
Creates more repulsion
b) d
z
2
d
xz
Creates less repulsion
Correlation of Terms of Free Ion and
O
h
Complexes
A
1g
+ E
g
+ T
1g
+ T
2g
9 G
T
1g
+ T
2g
+ A
2g
7 F
T
2g
+ E
g
5 D
T
1g
(no splitting) 3 P
A
1g
(no splitting) 1 S
Terms in O
h
Symmetry
Number of
States
Atomic
Term
Correlation of Terms of Free Ion and
O
h
d
1
and d
2
Complexes
-0.8A
0
0.2A
0
1.2A
0
Orgel Diagrams
Tanabe-Sugano Diagram of d
2
Configuration
Tanabe-Sugano Diagrams
For a given C/B value
A plot of energy E (in terms of B) vs. ligand field
splitting A
o
(in terms of B)
E = energy relative to the ground-state term (i.e.
ground state term energy = zero)
As A
o
increases, electrons tend to pair up, if possible
(i.e. change in spin multiplicity)
Electronic transition occurs from the ground state to
the next excited states with the same multiplicity (spin
selection rule)
Help on Tanabe-Sugano diagrams
http://wwwchem.uwimona.edu.jm:1104/courses/Tanabe-Sugano/
Non-crossing Rule
As the strength of the
interaction changes, states
of the same spin
degeneracy (multiplicity)
and symmetry CANNOT
cross.
Determine the
o
and B using Tanabe-
Sugano Diagram
28500/21500 ~ 1.32 at
A
0
/B ~ 32.8
32.8B = 21550 B = 657 cm
-1
A
0
/B = 32.8 A
0
= 21550 cm
-1
28500 21550
32.8
Ratio = 1.32
32.8
Nephelauxetic Effect
Nephelauxetic : cloud expanding
B is a measure of electronic repulsion
B(complex) < B(free ion)
B(complex)/B(free ion) < 1
Example: B for [Cr(NH
3
)
6
]
3+
= 657 cm
-1
B for Cr
3+
free ion ~ 1027 cm
-1
Electronic repulsion decreases as molecular orbitals are
delocalized over the ligands away from the metal
Nephelauxetic Series
| = B(complex)/B(free ion)
small | : large nephelauxetic effect, large delocalization, high
covalent character (soft ligands)
For a given metal center, ligands can be arranged in decreasing
order of |
| : F
-
> H
2
O > NH
3
> CN
-
, Cl
-
> Br
-
Intensities of Transitions
Electronic Transition:
interaction of electric field component E of
electromagnetic radiation with electron
Beers Law: absorbance A = log I
o
/I = cbc
c = concentration, M b = path length, cm
c = molar extinction coefficient, M
-1
cm
-1
Probability of Transition transition moment
fi

fi
= }
f
*
i
dt

f
: final state
i
: initial state
: - er electric dipole moment operator
Intensity of absorption
fi
2
Allowed Transition
fi
= 0
Forbidden Transition
fi
= 0
Spin Selection Rule
The electromagnetic field of the incident radiation
cannot change the relative orientation of the spins of
electrons in a complex
AS = 0, spin-allowed transitions
transition between states of same spin multiplicity
AS = 0, spin-forbidden transitions
transition between states of different spin multiplicity
Laporte Selection Rule
In a centrosymmetric molecule or ion (with symmetry
element i ), the only allowed transitions are those
accompanied by a change in parity (u g, g u)
Laporte (Symmetry) Allowed gu, ug
Laporte (Symmetry) Forbidden gxg , uxu
d orbitals have g character in O
h
all d-d transitions are Laporte forbidden
= - er : u function
d orbital : g function

fi
= }
f
*
i
dt
= } g x u x g = } u = 0
In T
d
, no i. Laporte rule is silent.
Intensities of Spectroscopic
Bands in 3d Complexes
Transition c
max
(M
-1
cm
-1
)
Spin-forbidden (and Laporte forbidden) < 1
Laporte-forbidden (spin allowed) 20 - 100
Laporte-allowed ~ 500
Symmetry allowed (charge transfer) 1000 - 50000
Relaxation of Laporte
Selection Rules
Depart from perfect symmetry
Ligand
Geometric Distortion
Vibronic coupling
Mixing of asymmetric vibrations
More intense absorption bands than
normal Laporte forbidden transitions
Move of electrons
between metal and
ligand orbitals
Very high intensity
LMCT: ligand to metal
MLCT: metal to ligand
Charge Transfer (CT) Transitions
Ligand to Metal Charge
Transfer (LMCT)
dt(M)pt (L) transitions are both spin
and symmetry allowed and therefore
are usually have much higher intensity
than d-d transitions.
d(M)p (L) LMCT of [Cr(NH
3
)
5
X]
2+
X
-
weaker field ligand than NH
3
A
0
reduced
Symmetry reduced, O
h
C
4v
energy level splitted
LMCT energy : MCl > MBr > MI
Comparison of
[Cr(NH
3
)
6
]
3+
and
[Cr(NH
3
)
5
X]
2+
d
0
Oxo Ions [MO
x
]
y-
d(M) p(O) Charge Transfer
LMCT energy
[MnO
4
]
-
(purple) < [TcO
4
]
-
< [ReO
4
]
-
(white)
[CrO
4
]
2-
(yellow) < [MoO
4
]
2-
< [WO
4
]
2-
(white)
[WS
4
]
2-
(red) < [WO
4
]
2-
(white)
dt(1
st
row T.M.) lower than dt(3
rd
row T.M.) in same
group
pt(E) higher down the same group
pt(O) lower than pt(S)
Effect of M and L on LMCT
dt
1
st
row T.M.
3
rd
row T.M.
2
nd
row T.M.
pt
L
dt
M
pt
S
O
Optical Electrnegativities
Optical Electrnegativities
variation in position of LMCT bands
v = | _
ligand
_
metal
| v
0
v
0
= 3.0 X 10
4
cm
-1
3.3 NH
3
2.1 Mo(V)
3.5 H
2
O 2.3 Rh(III) l.s.
3.0 2.5 I
-
1.8 - 1.9 Co(II)
3.3 2.8 Br
-
2.0 - 2.1 Ni(II)
3.4 3.0 Cl
-
2.3 Co(III) l.s.
4.4 3.9 F
-
1.8 - 1.9 Cr(III)
o t
Ligand T
d
O
h
Metal
Metal to Ligand Charge
Transfer (MLCT)
For metal ions in low oxidation state (dt
low in energy)
For ligands with low-lying t* orbitals,
especially aromatic ligands (e.g. di-
imine ligands such as bipy and phen)
Move of electrons
between metal and
ligand orbitals
Very high intensity
LMCT: ligand to metal
MLCT: metal to ligand
Charge Transfer (CT) Transitions
Luminescence
Phosphorescence
AS 0
Fluorescence
AS =0
Ruby:
Cr
3+
in alumina
Phosphorescence of [Ru(bipy)
3
]
2+
Spectra of f-block Complexes
Free-ion limit
f-orbitals are deep inside atoms.
Ligand show little effects
Sharp transitions
8
Tb
3+
9
Dy
3+
10
Ho
3+
11
Er
3+
12
Tm
3+
13
Yb
3+
14
Lu
3+
# of f
color-
less
Pink yellow pink red Green color-
less
color-
less
color
7
Gd
3+
6
Eu
3+
5
Sm
3+
4
Pm
3+
3
Nd
3+
2
Pr
3+
1
Ce
3+
0
La
3+
# of f
Pr
3+
(aq)
, f
2
Circular Dichroism Spectra
CD spectra can be observed for chrial
complexes, it can be used to infer the absolute
configuration of enantiomers