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the Period 4 transition metals

Usama El-Ayaan
Colors of representative compounds of the Period 4
transition metals
titanium oxidesodium chromatepotassiumferricyanidenickel(
II
) nitratehexahydratezinc sulfateheptahydratescandium
oxidevanadyl sulfatedihydratemanganese(
II
)chloridetetrahydratecobalt(
II
)chloridehexahydratecopper(
II
)sulfatepentahydrate
Usama El-Ayaan
Aqueous oxoanions of transition elements
M n I
I M n
V I M
n V I
I One of the most characteristicchemical
properties of theseelements is the occurrence of
multipleoxidationstates.
V(V)Cr(VI)Mn(VII)
Usama El-Ayaan
Effects of the metal oxidation state and of ligand
identity on color
[V(H
2
O)
6
]
2+
[V(H
2
O)
6
]
3+
[Cr(NH
3
)
6
]
3+
[Cr(NH
3
)
5
Cl]
2+
Usama El-Ayaan
Linkage isomers
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Complementary colour
Usama El-Ayaan
Usama El-Ayaan
The five d-orbitals in an octahedral field of ligands
Usama El-Ayaan
Splitting of d-orbital energies by an octahedral field of
ligands
∆
is the splitting energy
Usama El-Ayaan
The effect of ligand on splitting energy
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Electronic Spectroscopy of Transition Metal Complexes

Chemistry 412 Experiment 1
Usama El-Ayaan
What is electronic spectroscopy?

Absorption
Absorption of radiation leading to electronic transitions
within a molecule or complex
Absorption
[Ru(bpy)
3
]
2+
[Ni(H
2
O)
6
]
2+
1010
4
U V = h i g h e r e n e r g y t r a n
s i t i o n s -
b e t w e e n l i g a n d o r b i t a l
s v i s i b l e = l o w e r e n e r g y
t r a n s i t i o n s - b e t w e e n d -
o r b i t a l s o f t r a n s i t i o n m e t a l s -
between metal and ligand orbitals
UV400
λ/
nm
(wavelength)2
0
0
7
0
0 visible
~ 1 4
0 0
0 5 0
0 0
0 25 000UVvisible
ν/
cm
-1
(frequency)
−
Usama El-Ayaan
Absorption maxima in a visible spectrum have three
important characteristics1 . n u m b e r (ho
w many there are)This depends on the electron
configuration of the metal
centre2 . p o s i t i o n (what
wavelength/energy) of inter-electron
repulsion3 . i n t e n s i t y This depends on the
"allowedness" of the transitions which is described by
twoselection rules
Usama El-Ayaan
Selection Rules
In electronic spectroscopy there are three selection rules
whichdetermine whether or not transitions are formally
allowed:1 . S p i n s e l e c t i o n r u l e :
∆
S = 0allowed transitions: singlet
→
singletor triplet
→
tripletforbidden transitions: singlet
→
triplet or triplet
→
singlet
Singlet state:
All electrons in the molecule are spin-paired
Triplet state:
One set of electron spins is unpaired
Usama El-Ayaan
Selection rules
2.Laporte selection rule: there must be a ch
a n g e i n t h e p a r i t y (symmetry) of the complexLaporte-
allowed transitions:
g
→
u
Laporte-forbidden transitions:
g
→
g oru
→
u
Transition metal complexes get around thisrule through M-
L vibrations, whichtemporarily removes the center of
symmetry
g
stands for
gerade
–compound with a center of symmetry
u
stands for
ungerade
–compound without a center of
symmetry3 . S e l e c t i o n r u l e o f
∆
ℓ
=
±
1(
ℓ
is the azimuthal or orbital quantumnumber, where
ℓ
= 0 (s orbital), 1 (p orbital), 2 (d orbital),
etc.)allowed transitions: s
→
p, p
→
d, d
→
f, etc.forbidden transitions: s
→
s, d
→
d, p
→
f, etc.
Usama El-Ayaan
Energy of transitionsmolecular rotationslower energy( 0 . 0 1
-1 kJ mol
-1
)microwave radiationelectron transitionshigher
energy( 1 0 0 - 1 0
4
kJ mol
-1
)visible and UV radiationGround StateExcited
Statemolecular vibrationsmedium energy( 1 - 1 2 0 k J
mol
-1
)IR radiationDuring an electronic transitionthe complex
absorbs energyelectrons change orbitalthe complex changes
energy state
Usama El-Ayaan
[Ti(OH
2
)
6
]
3+
=d
1
ion, octahedral complex
white light400-800 nmblue: 400-490 nmyellow-green: 490-580
nmred: 580-700 nm
3+
Ti
Absorption of light
A
λ
/ nm
T h i s c o m p l e x h a s a l i g h t p u r p l e c o l
o u r i n solutionbecauseitabsorbsgreenli
ght
λ
max
= 510 nm
Usama El-Ayaan
e
g
t
2g
∆
o
h
ν
The energy of the absorption by [Ti(OH
2
)
6
]
3+
is the ligand-field splitting,
∆
o
GSESGSES
e
g
t
2g
d-d transition[Ti(OH
2
)
6
]
3+
λ
max
=510 nm
∆
o
is
∴
243 kJ mol
-1
20 300 cm
-1
An electron changes orbital; the ion changes energy
statecomplex in electronicGround State (GS)complex in
electronicexcited state (ES)
Usama El-Ayaan
Electron-electron repulsiond
2
ione
g
t
2g
x y x z y z z
2
x
2
-y
2
e
g
t
2g
x y x z y z z
2
x
2
-y
2
2
xz + z l o b e s o v e r l a p , l a r g e e l e c t r o n
repulsionlobes far apart,
s m a l l e l e c t r o n r e p u l s i o n xzxzyyThese two
electron configurations do not have the same energy
Usama El-Ayaan
Deriving term symbols in a free ion-an electron
is completely defined by 4 quantum numbersn= 1,2,3…
(energy and distance from the nucleus ie. what
shell)Electron configurations of the same energy are
collected together into termsl= 0, 1, 2…orbital
angular momentum (what sort {shape} of orbital, s, p,
d…)m
l
= -l…+l component of l (what kind of orbital, eg. for d: xy, xz…)m
s
= spin angular momentum (contribution from unpaired
electrons, spin 1/2)-an ion can be defined using ionic
quantum numbers made up of contributionsfrom all the
electrons in the ion…....…these define the
wholeion
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Russel Saunders CouplingL= 0, 1, 2…total orbital angular

momentum (term)M
L
= -L…+L component of L (M
L
=
Σ
m
l
)S= total spin quantum number (S =
Σ
s)Ionic quantum numbers:Each electronic state has its own
term symbol2S+1
L
spin
multiplicityL = 0 S t e r
m L = 1 P t e r m
L = 2 D t e r m L
= 3 F t e r m Within each
term, there can be several degenerate microstates with
different M
L
and M
S
M
s
= -S….+S component of S (M
S
=
Σ
m
s
)
Usama El-Ayaan
Microstates e.g. for a free d
2
ion
10 ways of arranging 2 electrons in 5 degenerate d-
orbitals (Hund's rules apply)
etcl o w r e p u l s i o n ( 7 m i c r o s t a t e s
) h i g h r e p u l s i o n ( 3 m i c r o s t a t e s
) xy + z
2
x y + x z x
2
-y
2
+z
2
xz + z
2
x y + y z x
2
-y
2
+
y z
y z
+
z
2
x z +
z x
2
-
2
+
x z
x
+
x
2
-
2
2S+1
L
spin multiplicityorbital angular momentum M
L
= -3,-2, -1, 0, 1, 2, 3M
L
= -1, 0, 1
Usama El-Ayaan
l o w r e p u l s i o n ( 7 m i c r o s t a t e s ) h
i g h r e p u l s i o n ( 3 m i c r o s t a t e s ) M
L
=
∑
m
l
For d-orbitals m
l
= -
2 -
1 0 1
2 x
2
-y
2
yzz
2
x z x y For M
L
= -
3 … . 3 L =
3 F t e r m For M
L
= -
1 … . 1 L =
1 P t e r m xy + z
2
x y + x z x
2
-y
2
+z
2
xz + z
2
x y + y z x
2
-y
2
+
y z
y z
+
z
2
x z + y z x
2
-y
2
+
x z
x y
+
x
2
-y
2
M
L
= -3, -2, -1, 0, 1, 2, 3M
L
= -1, 0, 1
Usama El-Ayaan
T o t a l s p i n S = n o . o f e
l e c t r o n s x s p i n o n a n
e l e c t r o n 2
x 1
/ 2
∴
S =1Spin multiplicity = (2S + 1) = 32S+1
L
F and P?For a free d
2
ion with two parallel spins there are two terms3
F
3
P
l o w e n e r
g y h i g h e
n e r g y
Usama El-Ayaan
3
P
3
F
∆
E
∆
E = 15 BStates of the samespin multiplicityWhich is the
Ground State?B is the Racah parameter and is a measure
of inter-electron repulsionwithin the whole ionRelative
strength of coupling interactions:M
S
=
Σ
m
s
>
M
L
=
Σ
m
l
>
M
L
-M
S
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1.States with the highest spin multiplicity (2S+1) will

be lowest in energy(S = no. of e
-
x spin 1/2)e.g. for a d
5
ion
6
S<
4
GDeriving the Ground State Term (Hund's rules) 2.Of two
states with the same S, the one with higher L is of
lower energyL = 0, S term; L = 1, P term; L = 2, D term; L =
3, F terme.g. for a d
2
ion
3
F<
3
PThese rules are only applicable to the ground state
Usama El-Ayaan
What are the ground state terms for the configurations p
2
and d
2
?p
2
:
1
D
3
P
1
SThe ground state must be
3
P because this has the largest spin multiplicityd
2
:
1
G
3
F
1
D
3
P
1
SThe ground state is either
3
F or
3
P because these have the largest spin multiplicityOf the
two,
3
F must be the ground state because it has the largest
value of L(when L = 2, P term; when L = 3, F term)
Usama El-Ayaan
Ground States in free ionsd
4
- 2 -
1 0 1 2
5
D
M
L
= -
2 … 2 L = 2 D
t e r m M
S
= 4 / 2 2
S + 1 =
5 d
3
- 2 -
1 0 1 2
4
F
M
L
= -
3 … 3 L = 3 F
t e r m M
S
= 3 / 2 2
S + 1 =
4 d
5
- 2 -
1 0 1 2
6
S
M
L
= 0 L
= 0
S t e r
m M
S
= 5 / 2 2
S + 1 =
6 d
6
- 2 -
1 0 1 2
5
D
M
L
= -
2 … . 2 L = 2 D
t e r m M
S
= 2 2
S + 1
= 5
Usama El-Ayaan
Ground States in free ionsd
7
- 2 -
1 0 1 2
4
F
M
L
= -3….3 L = 3 F termM
S
= 3 / 2 2
S + 1 =
4 --
3
F
d
9
- 2 -
1 0 1 2
2
D
M
L
= -3….3 L = 3 Fterm M
S
= 2 / 2 2
S + 1 =
3 M
L
= -
2 … 2 L =
2 D t e r
m M
S
= 1 / 2 2
S + 1 =
2
Usama El-Ayaan
Ground State Terms for all electron configurationsGround
Stated
1
d
92
Dd
2
d
83
F
3
Pd
3
d
74
F
4
Pd
4
d
65
Dd - d t r a n s i t i o n s i n h i g h s p i n c o m p l e x e s
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2
E
g
E f f e c t o f a c r y s t a l f i e l d o n t h e f r e
e i o n t e r m o f a d
1
complext e t r a h e d r a l f i
e l d f r e e i o n o c t a h
e d r a l f i e l d d
1
≅≅≅≅
d
62
T
2g2
T
22
E6Dq4Dq
2
D
Usama El-Ayaan
∆∆∆∆
2
E
g2
EnergyE n e r g y l e v e l d i a g r a m f o r d
1
i o n s i n a n O
h
field
2
T
2g
ligandfieldstrength,
∆
oct
Ford
6
ions in an O
h
field, the splitting is the same, but the multiplicity of the
states is 5,
ie
5
E
g
and
5
T
2g
Usama El-Ayaan
A
ν
/ cm
-1
-
30 00020 00010 000
d
1
oct
[Ti(OH
2
)
6
]
3+
46
9
2
E
g
2
T
2g2
E
g2
T
2g2
D
∆∆∆∆
EL F s t r e n g t h
, ,,
0
∆∆
Dd
4
,
d
9
tetrahedralT
2g
or T
2
T
2g
orT
2
d
4
,
d
9
octahedralE
g
or Ed
1
,
d
6
tetrahedralE
g
orEd
1
,
d
6
octahedral
∆∆∆∆
Usama El-Ayaan
The Jahn-Teller Distortion: Any non-linear molecule
in a degenerate electronic statewill undergo distortion to lower
it's symmetry and lift the degeneracyd
34
A
2g
d
5
(high spin)
6
A
1g
d
6
(low spin)
1
A
1g
d
83
A
2g
Degenerate electronic ground state:T or ENon-degenerate
ground state:A
A
ν
/ cm
-1
-
30 00020 00010 000
[Ti(H
2
O)
6
]
3+
,d
1
2
T
2g2
E
g2
B
1g2
A
1g
Usama El-Ayaan
RacahParameters d
7
tetrahedral complex15 B'= 1 0 9 0 0 c m
-1
B'= 7 2 7 c m
-1
[CoCl
4
]
2-
[Co(H
2
O)
6
]
2+
d
7
octahedral complex15 B'= 1 3 8 0 0 c m
-1
B'= 9 2 0 c m
-1
Free ion [Co
2+
]:B= 9 7 1 c m
-1
B'= 0 . 9 5 BB'= 0 . 7 5 BNephelauxetic ratio,
ββββββββ
is a measure of the decrease in electron-electron
repulsion on complexation
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-some covalency in M-L bonds –M and L share

electrons-effective size of metal orbitals increases-
electron-electron repulsion decreasescloud
expandingT h e N e p h e l a u x e t i c E f f e c t Nephelauxetic ser
ies of ligandsF
-
<H
2
O < NH
3
< en < [oxalate]
2-
< [NCS]
-
< Cl
-
< Br
-
<I
-
Nephelauxetic series of metal ionsMn(II) <Ni(II) Co(II)
< Mo(II) > Re (IV) < Fe(III) < Ir(III) < Co(III) < Mn(IV)
Usama El-Ayaan
Selection RulesTransition
εεεε
complexes
S p i n f o r b i d
d e n 1 0
-3
–1Many d
5
O
h
cxsLaporte forbidden [Mn(OH
2
)
6
]
2+
Spin
allowedL a p o r t e
f o r b i d d e n
1 –
1 0 M a n y O
h
cxs[Ni(OH
2
)
6
]
2+
1 0 –
1 0 0 S o m e s q u a r
e p l a n a r c x s [PdCl
4
]
2-
1 0 0 – 1 0 0 0 6 -
c o o r d i n a t e c o m p l e x e s o f l o
w s y m m e t r y , many square planar cxs
particularly withorganic
ligandsS p i n a l l
o w e d 1 0
2
–10
3
Some MLCT bands in cxs with unsaturated ligandsLaporte
allowed10
2
–10
4
Acentric complexes with ligands such as acac, orwith P
donor atoms10
3
–10
6
Many CT bands, transitions in organic species
Usama El-Ayaan
e
g
t
2g
e
g
t
2g
I
-
< Br
-
<S
2-
< SCN
-
< Cl
-
< NO
3-
<F
-
< OH
-
< ox
2-
<H
2
O < NCS
-
< CH
3
CN < NH
3
< en < bpy< phen < NO
2-
< phosph < CN
-
< CO
The Spectrochemical Series
∆∆
weak field ligandse.g. H
2
Ohigh spin complexesstrong field ligandse.g. CN
-
low spin complexesThe Spin Transition
Usama El-Ayaan
Tanabe-Sugano diagramsE/B
2
T
2g4
A
1g,4
E
4
T
2g4
T
1g2
A
1g4
T
2g2
E
2
T
1g2
A
1g4
E
g
All terms includedGround state assigned to E = 0Higher
levels drawn relative to GSEnergy in terms of BHigh-spin
and low-spin configurationsd
5
∆
/B
4
T
2g4
T
1g2
T
2g6
A
1g4
A
2g,2
T
1g
Critical value of
∆
W E A K F I E L
D S T R O N G F
I E L D
Usama El-Ayaan
Tanabe-Sugano diagram for d
2
ionsE/B[V(H
2
O)
6
]
3+
: Three spin allowed transitions
ν νν ν
1
= 17 800 cm
-1
visible
ν νν ν
2
= 25 700 cm
-1
visible
10 000
ε
30 000
ν/
cm
-1
−
1020 0005
∆
/B
ν νν ν
3
= obscured by CT transition in
UV2 5 7 0 0 = 1 . 4 4 17 800
∆
/B=32
ν νν ν
3
= 2.1
ν νν ν
1
= 2.1 x 17 800
∴ν νν ν
3
= 37 000 cm
-1
= 32
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E/B
ν νν ν
1
= 17 800 cm
-1
ν νν ν
2
= 25 700 cm
-1
ν νν ν ν νν ν
2
E/B = 43 cm
-1
-1
∆
/B= 32 E/B = 43 cm
-1
E = 25 700 cm
-1
B = 6 0
0 c m
-1
∆
o
/ B=32
∆
o
= 1 9 2 0 0 c m
-1
Usama El-Ayaan
Tanabe-Sugano diagram for d
3
ionsE/B[Cr(H
2
O)
6
]
3+
: Three spin allowed transitions
ν νν ν
1
= 17 400 cm
-1
visible
ν νν ν
2
= 24 500 cm
-1
visible
ν νν ν
3
= obscured by CT
transition2 4 5 0 0 = 1 . 4 1 17
400
∆
/B=24
∆
/B
ν νν ν
3
= 2.1
ν νν ν
1
= 2.1 x 17 400
∴ν νν ν
3
= 36 500 cm
-1
= 24
Usama El-Ayaan
Calculating
ν
3
E/B
ν νν ν
1
= 17 400 cm
-1
ν νν ν
2
= 24 500 cm
-1
When
ν νν ν
1
= E =17 400 cm
-1
E/B = 24so B = 725 cm
-1
When
ν νν ν
2
= E =24 500 cm
-1
∆
/B= 24E/B = 34 cm
-1
E/B = 24 cm
-1
=so B = 725 cm
-1
If
∆
/B =24
∆
= 24 x 725 = 17 400 cm
-1
Usama El-Ayaan
TiF
4
d
0
ionTiCl
4
d
0
ionTiBr
4
d
0
ionTiI
4
d
0
iond
0
and d
10
ion have no d-d transitionsZn
2+
d
10
iond
0
and d
10
ionswhitewhiteorangedark brownwhite[MnO
4
]
-
M n ( V I I ) d
0
ion[Cr
2
O
7
]
-
C r ( V I ) d
0
ion[Cu(MeCN)
4
]
+
C u ( I ) d
10
ion[Cu(phen)
2
]
+
C u ( I ) d
10
ionextremely purplebright orangecolourlessdark orange
Charge Transfer Transitions
Usama El-Ayaan
Charge Transfer TransitionsLigand-to-metal charge
transferLMCT transitionsMetal-to-ligand charge
transferMLCT transitionsL
π
∗
e
g*
d-d transitionsMdL
π
L
σ
t
2g*
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Transition Metals, Compounds and Complexes or Electronic

Spectroscopy of Transition Metal Complexes
Dr. E.R.
Schofield e c u r e n e r p r e a o n
o w e a
e s p e c r a Electronic spectra from
Orgel diagrams Orgel diagram for d
2
,d
3
,d
7
,d
8
ions
Usama El-Ayaan
Energyd
1
≡≡≡≡
d
6
d
4
≡≡≡≡
d
9
Orgel diagram for d
1
,
d
4
,
d
6
,
d
9
D
or
ET
2g
or
T
2
E
g
ligandfieldstrength0
∆∆
d
4
,
d
9
tetrahedral
or
T
2
E
g
or
d
4
,
d
9
octahedralEd
1
,
d
6
tetrahedralT
2g
d
1
,
d
6
octahedral
Usama El-Ayaan
A
ν
/ cm
-1
-
30 00020 00010 000
d
1
oct
[Ti(OH
2
)
6
]
3+
46
9
2
E
g
2
T
2g2
E
g2
T
2g2
D
∆∆∆∆
EL F s t r e n g t h
, ,,
0
∆∆
Dd
4
,
d
9
tetrahedralT
2g
or T
2
T
2g
orT
2
d
4
,
d
9
octahedralE
g
or Ed
1
,
d
6
tetrahedralE
g
orEd
1
,
d
6
octahedral
∆∆∆∆
Usama El-Ayaan
Effect of a ligand field on Ground State TermsGSd
1
d
92
Dd
2
d
83
F
3
Pd
3
d
74
F
4
Pd
4
d
65
Dd
56
S
DT
2(g)
and E
(g)
free ion ligand field
GSd
1
d
92
Dd
2
d
83
F
3
Pd
3
d
74
F
4
Pd
4
d
65
Dd
56
S
PF
free ion ligand field
?
Usama El-Ayaan
Octahedrald
2
complex
3
P: high repulsionIn a LF, these orbitals are unaffected
3
F : l o w r e p u l s i o n In a LF, orbitals in the t
2g
set go down in energy, orbitals in the e
g
set go up in energyxz + z
2
yz + z
2
xy + x
2
-y
23
T
1g
d
2
≅≅≅≅
d
7
x
2
-y
2
+z
2
x
2
-y
2
+ yzx
2
-y
2
+ xzxy + z
2
xy +xzxy +yzxz +yz
3
A
2g3
T
2g3
T
1g
e
g
e
g
singly degenerate, high energye
g
t
2g
triply degenerate, medium energyt
2g
t
2g
triply degenerate, low energy
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Octahedrald
3
complex
4
P: high repulsionIn a LF, these orbitals are unaffected
4
T
1g4
F: lowrepulsion
2
d
3
≅≅≅≅
d
8
(same terms, different spin)
4
T
1g4
T
2g4
A
2g
Usama El-Ayaan
Energy
Orgeldiagramford
2
,d
3
,d
7
,d
8
ionsQuantum MixingFPT
1
or T
1g
T
1
or T
1g
A
2
or A
2g
T
1
or T
1g
T
2
or T
2g
Ligand field strength(Dq)d
2
,d
7
t e t r a h
e d r a l d
2
,d
7
octahedrald
3
,d
8
octahedral d
3
,d
8
tetrahedral0T
2
or T
2g
A
2
or A
2g
T
1
or T
1g
Usama El-Ayaan
PEnergy level diagram for oct d
2
,d
7
, tet d
3
,d
8
1 5 B ' 15B15 B > 15 B'x10DT
1(g)
A
2(g)
Fx6Dq2DqT
1(g)
T
2(g)
Usama El-Ayaan
Calculating B' and xd
7
octahedral complex
4
A
2g4
T
1g
1 0 D q x1 5 B ' A
[Co(H
2
O)
6
]
2+
ν νν ν
2
ν νν ν
3
ν νν ν
1
ν νν ν
2
ν νν ν
3
v / cm
-1
4
T
1g4
T
2g
6Dq2Dqx
ν νν ν
1
2 5 0 0 0 2 0 0 0 0 1
5 0 0 0 1 0 0 0 0
ν νν ν
1
= 8 000 cm
-1
ν νν ν
2
= 16 000 cm
-1
ν νν ν
3
= 19 400 cm
-1
Usama El-Ayaan
FP
Energy
Orgeldiagramford
2
,d
3
,d
7
,d
8
ionsA
2
or A
2g
T
1
or T
1g
T
2
or T
2g
T
1
or T
1g
T
1
or T
1g

2
,d
7
t e t r a h
e d r a l d
2
,d
7
octahedrald
3
,d
8
octahedral d
3
,d
8
tetrahedral0T
2
or T
2g
A
2
or A
2g
T
1
or T
1g
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Px1 0 D q T
1(g)
A
2(g)
Energy level diagram for oct d
2
,d
7
, tet d
3
,d
8
ν νν ν
1
:x+8 Dq
ν νν ν
2
:2 x+6 Dq+15 B'
ν νν ν
3
:x+18 Dq
ν νν ν
2
ν νν ν
3
ν νν ν
1
:T
2(g)
T
1(g)
ν νν ν
2
:T
1(g)
(P)
T
1(g)
ν νν ν
3
:A
2(g)
T
1(g)
F1 5 B ' 15Bx6Dq2DqT
1(g)
T
2(g)
ν νν ν
1
Usama El-Ayaan
Transition Metal Complexes
Housecroft and Sharpe, p. 20
Usama El-Ayaan
Metal
d
orbi tals –octahedral metal compl exes
M = metalL = ligand
t
2g
orbi tals –point between the ligands –
π
symmetrye
g
orbi tals –point at theligands –
σ
symmetry
Usama El-Ayaan
UV-visible spectra of transition metal complexes
Transition metal complexes commonlyexhibit UV-visible
spectra containingbothweak “
d-d
”(
ε
< 100)andstrong“charge-transfer” (
ε
> 1000)bandswhich are characteristic of
the natureo o t t e m e
t a a n t e g a n
s
Shriver, Langford & Atkins (2
nd
ed), p. 582
Usama El-Ayaan
Selection Rules
In electronic spectroscopy there are three selection rules
whichdetermine whether or not transitions are formally
allowed:1 . S p i n s e l e c t i o n r u l e :
∆
S = 0allowed transitions: singlet
→
singletor triplet
→
triplet o r e n t r a n s t o n s :
s n g e t
→
t r p e t o r t r p e t
→
s n g e t Changes in spin multiplicity are forbidden
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Selection rules
2.Laporte selection rule: there must be a ch
a n g e i n t h e p a r i t y (symmetry) of the complexLaporte-
allowed transitions:
g
→
u
Laporte-forbidden transitions:
g
→
g oru
→
u
Transition metal complexes get around thisrule through M-
L vibrations, whichtemporarily removes the center of
symmetry
g
stands for
gerade
–compound with a center of symmetry
u
stands for
ungerade
–compound without a center of
symmetry3 . S e l e c t i o n r u l e o f
∆
ℓ
=
±
1(
ℓ
is the azimuthal or orbital quantumnumber, where
ℓ
= 0 (s orbital), 1 (p orbital), 2 (d orbital),
etc.)allowed transitions: s
→
p, p
→
d, d
→
f, etc.forbidden transitions: s
→
s, d
→
d, p
→
f, etc.
Usama El-Ayaan
Crystal field theory –
d
orbitals split into two sets
e
g
t
2g
Usama El-Ayaan
Crystal Field Splitting
To promote an electron from the lower
d
orbital to the higher
d
orbitalrequires energy equal to
∆
oct
, the “crystal field splitting energy”
Usama El-Ayaan
Spectrochemical Series
Spectrochemical Series (the effect of the ligand set on the
magnitudeof
∆
o
)I
-
< Br
-
< Cl
-
<F
-
<O
2-
< OH
-
<H
2
O < NH
3
< NO
2-
< CN
-
< PR
3
< CO
σ
-donor ligands
π
-donor ligands increase the energy of the t
2g
orbitals
π
-acceptor ligands decrease the energy of the t
2g
orbitals
Usama El-Ayaan
Visible spectra of octahedral Ni(II) complexes

[Ni(NH
3
)
6
]
2+
1 0 0
0 3
0 0
n m [Ni(H
2
O)
6
]
2+
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Tanabe-Sugano diagrams
d
3
d
2
Shriver, Langford & Atkins

ground state states
Usama El-Ayaan
UV-visible spectrum of a Chromium(III) complex
Spin-allowed transitionsQuartet
→
QuartetS i n - f o r b i d d e n t r a n s i t i o n s

nd
ed), p. 582
Quartet
→
Doublet
Usama El-Ayaan
d-d
transitions in
d
3
metal complexes
For a
d
3
metal ion, such as Cr
3+
there is one electron in each ofthe three t
2g
orbitals, while thee
g
orbitals are empty
d
3
nd
ed), p. 594
t
2gg
t
2g
e
g
d-dtransiton
Usama El-Ayaan
Excitation of
d
electrons
yzzy
Electrongoes fromthe d
xy
orbital into aElectrongoes fromthe d
xz
orbital into a
nd
ed), p. 590
xx
d
z
2
orbital*requires achange inplanes (xy toz)d
z
2
orbital*much lessrelocation ofthe electron
Usama El-Ayaan
Tanabe-Sugano diagram –
d
2
ion
Tanabe-Sugano diagram for a
d
2
ion, such as V
2+3
T
1g
→
3
T
2g3
T
1g3
T
1g
(F)
→
3
T
1g
(P)
3
T
1g
→
3
A
2g
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Jahn-Teller distortions
e.g. [Ti(H
2
O)
6
]
3+
d
1
electronic configurationWhen a set of degenerate orbitals
are unevenly filled, then a perturbationof the molecular
structure will occur so that the degeneracy is removed
e
g
t
2g
d
z2
d
xz
,d
yz
d
xy
d
x2-y2
ν
1
ν
2
d
Usama El-Ayaan
[Ti(H
2
O)
6
]
3+
visible spectrum
ν
1
ν
2
5 0 0 4
0 0 600
[Ti(H
2
O)
6
]
3+
λ
, nm
Usama El-Ayaan
Visible spectrum of [Mn(H
2
O)
6
]
2+
(1 M solution)
Mn(H
2
O)
62+
is a “high-spin”
d
5
ion (t
2g3
e
g2
) andtherefore all
d
-
d
transitions are spin-forbiddenAll of the transitionshave
ε
values of << 1,(very weak)
Brisdon, p.
Usama El-Ayaan
Charge-Transfer
Ligand-to-MetalCharge Transfer(LMCT)
nd
ed), p. 595
Metal-to-LigandCharge Transfer(MLCT)
Charge transfer bands areallowed transitions, with
ε
values > 10,000
Usama El-Ayaan
Ligand-to-Metal Charge Transfer
•Occurs with metals in high oxidation states (few
d
electrons)complexed by ligands which are good electron-
donors
OMnOOO
Permanganate anionManganese(VII) has no
d
electrons,while theO
2-
(oxide) ligands donate lonepairs of electrons to form
double bonds
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UV-Visible spectrum of MnO

4-
L
π→
M(t
2g
)L
π→
M(e
g
)
Usama El-Ayaan
Metal-to-Ligand Charge Transfer (MLCT)
•Occurs with metals in low oxidation states (lots of
d
electrons)complexed by ligands which are good electron-
acceptorsRuthenium(II)
Housecroft and Sharpe, p. 208Ru(2,2’-bipyridine)
32+
as e
-
2,2’-bipyridineis a good
π
-acceptor ligand
Usama El-Ayaan
Visible spectrum of Ru(2,2’-bipyridine)
32+
[Ru(bpy)
3
]
2+
MLCT
λ
max
= 452 nm
ε
= 14,600 M
-1
cm
-1
Usama El-Ayaan
Coordination Chemistry
Usama El-Ayaan
Electronic configurations of multi-electron atoms Russell-
Saunders (or LS) coupling
For each 2p electron n
= 1;
l
=1
m
l
= -1, 0, +1
m
s
=
±
1/2
For the multi-electronatom L
= total orbital angular momentum quantum number
S
= total spin angular momentum quantum numberSpin
multiplicity = 2S+1=
-
L
, … , …
M
S
=
∑
m
s
(
S
,
S-1
, …,0,…
-S
)
M
L
/M
S
d efin e micro statesand L/S define states(collections of
microstates) Groups of microstates with the same energy are
called terms
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before we did:
p
2
M
L
&M
S
MicrostateTableStates (
S,P,D)
Spin multiplicity
Terms
3
P,
1
D,
1
S Ground state term
3
P
Usama El-Ayaan
For metal complexes we need to consider d
1
-d
10
d
23
F,
3
P,
1
G,
1
D,
1
S For 3 or more electrons, this is a long tedious process
But luckily this has been tabulated before…
Usama El-Ayaan
Transitonsbetweenelectronictermswilgiveriseotspectra
Usama El-Ayaan
Selection rules
(determine intensities)
Laporte rule g
→
g forbidden (that is, d-d forbidden) but g
→
u allowed (that is, d-p allowed) Spin rule Transitions between
states of different multiplicitiesforbidden Transitions between
states of same multiplicitiesallowed
These rules are relaxed by molecular vibrations, and spin-orbit
coupling
Usama El-Ayaan
Group theory analysis of term splitting
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High Spin Ground States

d
n
F r e e i o n G S O c t . c
o m p l e x T e t c o m p l e x
d
01
St
2g0
e
g0
e
0
t
20
d
12
Dt
2g1
e
g0
e
1
t
20
d
23
Ft
2g2
e
g0
e
2
t
20
d
34
Ft
2g3
e
g0
e
2
t
21
d
45
Dt
2g3
e
g1
e
2
t
22
An e electronsuperimposedon a
sphericaldistributionenergiesreversedbecausetetrahedral
d
56
St
2g3
e
g2
e
2
t
23
d
65
Dt
2g4
e
g2
e
3
t
23
d
74
Ft
2g5
e
g2
e
4
t
23
d
83
Ft
2g6
e
g2
e
4
t
24
d
92
Dt
2g6
e
g3
e
4
t
25
d
101
St
2g6
e
g4
e
4
t
26
Holes: d
n
=d
10-n
and neglecting spin d
n
=d
5+n
; samesplitting but reversed energies because positive.A t
2
hole in d
5
,reversed energies,reversed againrelative tooctahedral
since tet.Holes in d
5
and d
10
,reversingenergiesrelative tod
1
Expect oct d
1
and d
6
to behave same as tet d
4
and d
9
Expect oct d
4
and d
9
(holes), tet d
1
and d
6
to be reverse of oct d
1
Usama El-Ayaan
Energyd
1
≡≡≡≡
d
6
d
4
≡≡≡≡
d
9
Orgel diagram for d
1
,
d
4
,
d
6
,
d
9
D
or
ET
2g
or
T
2
E
g
ligandfieldstrength0
∆∆
d
4
,
d
9
tetrahedral
or
T
2
E
g
or
d
4
,
d
9
octahedralEd
1
,
d
6
tetrahedralT
2g
d
1
,
d
6
octahedral
Usama El-Ayaan
FP
Energy
Orgeldiagramford
2
,d
3
,d
7
,d
8
ionsA
2
or A
2g
T
1
or T
1g
T
2
or T
2g
T
1
or T
1g
T
1
or T
1g

2
,d
7
t e t r a h
e d r a l d
2
,d
7
octahedrald
3
,d
8
octahedral d
3
,d
8
tetrahedral0T
2
or T
2g
A
2
or A
2g
T
1
or T
1g
Usama El-Ayaan
d
2
3
F,
3
P,
1
G,
1
D,
1
S
Real complexes
Usama El-Ayaan
Tanabe-Sugano diagrams
d
2
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Electronic transitions and spectra

Usama El-Ayaan
Otherconfigurations
d
1
d
9
d
3
d
2
d
8
Usama El-Ayaan
Otherconfigurations
d
3
The limit between high spin and low spin
Usama El-Ayaan
Determining
∆
o
from spectra
d
1
d
9
One transition allowed of energy
∆
o
Usama El-Ayaan
mixing
Determining
∆
o
from spectra
Lowest energy transition =
∆
o
mixing
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Gro und statemixin g

E(
T
1g
→
A
2g
) - E (
T
1g
→
T
2g
)=
∆
o
Usama El-Ayaan
The d
5
case
All possible transitions forbidden Very weak signals, faint color
Usama El-Ayaan
Someexamplesofspectra
Usama El-Ayaan
Charge transfer spectra

LMCT
Ligand character Metal character
MLCT
Metal character Ligand character
Muchmoreintensebands
Usama El-Ayaan

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the Period 4 transition metals

Electronic Spectroscopy of Transition Metal Complexes

What is electronic spectroscopy?

Russel Saunders CouplingL= 0, 1, 2…total orbital angular

1.States with the highest spin multiplicity (2S+1) will

-some covalency in M-L bonds –M and L share

Transition Metals, Compounds and Complexes or Electronic

Ligand field strength(Dq)d

Visible spectra of octahedral Ni(II) complexes

Shriver, Langford & Atkins

Shriver, Langford & Atkins (2

UV-Visible spectrum of MnO

High Spin Ground States

Ligand field strength(Dq)d

Electronic transitions and spectra

Gro und statemixin g

Charge transfer spectra

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