The Period 4 transition metals

Colors of representative compounds of the Period 4 transition metals

nickel(II) nitrate
sodium chromate
hexahydrate
potassium zinc sulfate
titanium oxide
ferricyanide heptahydrate

scandium oxide manganese(II) copper(II)

chloride sulfate
vanadyl sulfate tetrahydrate cobalt(II) pentahydrate
dihydrate chloride
hexahydrate
 Aqueous oxoanions of transition elements

One of the most characteristic

chemical properties of these
elements is the occurrence of
multiple oxidation states.

Mn(II) Mn(VI) Mn(VII)

Mn(VII)
Cr(VI)
V(V)
Effects of the metal oxidation state and of ligand identity on
color

[V(H2O)6]2+ [V(H2O)6]3+

[Cr(NH3)6]3+ [Cr(NH3)5Cl ]2+

Linkage isomers
An artist’s wheel
The five d-orbitals in an octahedral field of ligands
Splitting of d-orbital energies by an octahedral field of ligands

 is the splitting energy

The effect of ligand on splitting energy
Electronic Spectroscopy of Transition Metal Complexes

Chemistry 412 Experiment 1

What is electronic spectroscopy?

Absorption of radiation leading to electronic transitions within a molecule or complex

Absorption
Absorption
[Ru(bpy)3]2+ [Ni(H2O)6]2+
104
10

~14 000 25 000 50 000

200 400 700

UV visible visible UV

nm (wavelength) 
cm-1 (frequency)

UV = higher energy transitions - between ligand orbitals

visible = lower energy transitions - between d-orbitals of transition metals
- between metal and ligand orbitals
Absorption maxima in a visible spectrum have three important characteristics

1. number (how many there are)

This depends on the electron configuration of the metal centre

2. position (what wavelength/energy)

This depends on the ligand field splitting parameter, oct or tet and on the degree
of inter-electron repulsion

3. intensity

This depends on the "allowedness" of the transitions which is described by two

selection rules
Energy of transitions
Excited State

molecular rotations
lower energy
(0.01 - 1 kJ mol-1)
microwave radiation

electron transitions
higher energy
(100 - 104 kJ mol-1) Ground State
visible and UV radiation

molecular vibrations
medium energy
(1 - 120 kJ mol-1)
IR radiation

During an electronic transition

the complex absorbs energy
electrons change orbital
the complex changes energy state
Absorption of light

[Ti(OH2)6]3+ = d1 ion, octahedral complex

white light
3+ 400-800 nm

blue: 400-490 nm
Ti
yellow-green: 490-580 nm
red: 580-700 nm

This complex is has a light purple colour

in solution because it absorbs green light

 / nm

max = 510 nm
 The energy of the absorption by [Ti(OH2)6]3+ is the ligand-field splitting, o

ES ES

eg eg
h
GS o GS
t2g t2g

complex in electronic d-d transition complex in electronic

Ground State (GS) excited state (ES)

[Ti(OH2)6]3+ max = 510 nm o is  243 kJ mol-1

20 300 cm-1

An electron changes orbital; the ion changes energy state

d2 ion Electron-electron repulsion

eg eg
z
2 x2-y2 z
2 x2-y2

t2g t2g
xy xz yz xy xz yz

xz + z2 xy + z2
z
z

y
y
x
x

lobes overlap, large electron repulsion lobes far apart, small electron repulsion
These two electron configurations do not have the same energy
Which is the Ground State?

3
P
States of the same
E
spin multiplicity
3
F

 E = 15 B

B is the Racah parameter and is a measure of inter-electron repulsion

within the whole ion

Relative strength of coupling interactions:

MS =  ms > ML =  ml > ML - M S
Effect of a crystal field on the free ion term of a d1 complex

d1  d6

tetrahedral field free ion octahedral field

2
Eg
2
T2 6 Dq
2
D

4 Dq
2
E 2
T2g
 Energy level diagram for d1 ions in an Oh field

Energy 2
Eg


2
D

2
T2g

ligand field strength, oct

For d6 ions in an Oh field, the splitting is the same, but the multiplicity of the states is 5,

ie 5Eg and 5T2g

d1 oct A [Ti(OH2)6]3+
2
Eg

Eg  2T2g
2


2
D

2
T2g
10 000 20 000 30 000

-/ cm-1

Orgel diagram for d1, d4, d6, d9

E Eg or E
T2g or T2

D


T2g or T2
Eg or E

 d1, d6 tetrahedral 0 d1, d6 octahedral 

d4, d9 octahedral d4, d9 tetrahedral
LF strength
The Jahn-Teller Distortion: Any non-linear molecule in a degenerate electronic state
will undergo distortion to lower it's symmetry and lift the degeneracy

Degenerate electronic ground state: T or E

Non-degenerate ground state: A d3 4

A2g
d5 (high spin) 6
A1g
d6 (low spin) 1
A1g
d8 3
A2g

2
B1g
A
Eg
2
[Ti(H2O)6]3+, d1
2
A1g

2
T2g

-/ cm-1
10 000 20 000 30 000
Racah Parameters

Free ion [Co2+]: B = 971 cm-1

[Co(H2O)6]2+ [CoCl4]2-

d7 octahedral complex d7 tetrahedral complex

15 B' = 13 800 cm-1 15 B' = 10 900 cm-1

B' = 920 cm-1 B' = 727 cm-1

B' = 0.95 B' = 0.75

B B

Nephelauxetic ratio, 

 is a measure of the decrease in electron-electron repulsion on complexation

 The Nephelauxetic Effect cloud expanding

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

-effective size of metal orbitals increases
-electron-electron repulsion decreases

Nephelauxetic series of ligands

F- < H2O < NH3 < en < [oxalate]2- < [NCS]- < Cl- < Br- < I-

Nephelauxetic series of metal ions

Mn(II) < Ni(II) Co(II) < Mo(II) > Re (IV) < Fe(III) < Ir(III) < Co(III) < Mn(IV)
 Selection Rules

Transition  complexes

Spin forbidden 10-3 – 1 Many d5 Oh cxs

Laporte forbidden [Mn(OH2)6]2+

Spin allowed
Laporte forbidden 1 – 10 Many Oh cxs
[Ni(OH2)6]2+

10 – 100 Some square planar cxs

[PdCl4]2-

100 – 1000 6-coordinate complexes of low symmetry,

many square planar cxs particularly with
organic ligands

Spin allowed 102 – 103 Some MLCT bands in cxs with unsaturated ligands
Laporte allowed
102 – 104 Acentric complexes with ligands such as acac, or
with P donor atoms

103 – 106 Many CT bands, transitions in organic species

 The Spectrochemical Series
eg

eg I- < Br- < S2- < SCN- < Cl-< NO3- < F- < OH- < ox2-
 
t 2g < H2O < NCS < CH3CN < NH3 < en < bpy
-

< phen < NO2- < phosph < CN- < CO

t 2g
weak field ligands strong field ligands
e.g. H2O e.g. CN-

high spin complexes low spin complexes

The Spin Transition

 d5 Tanabe-Sugano diagrams
4
T2g

2
A1g
E/B
4
T1g
4
Eg All terms included
4
T2g Ground state assigned to E = 0
4
A1g, 4E
2
A1g
Higher levels drawn relative to GS
2
T1g Energy in terms of B
T2g
2 High-spin and low-spin configurations
Eg
2

4
A2g, 2T1g Critical value of 

4
T2g

6
A1g
4
T1g

2
T2g

WEAK FIELD /B STRONG FIELD

Tanabe-Sugano diagram for d2 ions 10

[V(H2O)6]3+: Three spin allowed transitions


5

E/B
30 000 20 000 10 000

cm-1

1 = 17 800 cm-1 visible

2 = 25 700 cm-1 visible
3 = obscured by CT transition in UV

25 700 = 1.44 /B = 32

17 800

3 = 2.11 = 2.1 x 17 800

 3 = 37 000 cm-1
/B = 32
 E/B

1 = 17 800 cm-1
2 = 25 700 cm-1

2
E/B = 43 cm-1

E/B = 30 cm-1 1

E/B = 43 cm-1 E = 25 700 cm-1

B = 600 cm-1
o / B = 32
o = 19 200 cm-1 /B = 32
Tanabe-Sugano diagram for d3 ions
1 = 17 400 cm-1 visible
[Cr(H2O)6]3+: Three spin allowed transitions
2 = 24 500 cm-1 visible
E/B 3 = obscured by CT transition

24 500 = 1.41
17 400

/B = 24

3 = 2.11 = 2.1 x 17 400

 3 = 36 500 cm-1

/B = 24
 Calculating 3
1 = 17 400 cm-1
2 = 24 500 cm-1
E/B
When 1 = E =17 400 cm-1
E/B = 24
so B = 725 cm-1

When 2 = E =24 500 cm-1

E/B = 34

E/B = 34 cm-1 so B = 725 cm-1

E/B = 24 cm-1
If /B = 24
 = 24 x 725 = 17 400 cm-1

/B = 24
d0 and d10 ions d0 and d10 ion have no d-d transitions

Zn2+ d10 ion white

TiF4 d0 ion white

TiCl4 d0 ion white
orange
TiBr4 d0 ion
dark brown
TiI4 d0 ion

[MnO4]- Mn(VII) d0 ion extremely purple

[Cr2O7]- Cr(VI) d0 ion bright orange

[Cu(MeCN)4]+ Cu(I) d10 ion colourless

[Cu(phen)2]+ Cu(I) d10 ion dark orange

Charge Transfer Transitions

Metal-to-ligand charge transfer Ligand-to-metal charge transfer
MLCT transitions LMCT transitions

Charge Transfer Transitions

d-d transitions
L
eg*

t2g*

Md
L

L