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

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 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)

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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

Δ is the splitting energy

The effect of ligand on splitting energy
 The color of [Ti(H2O)6]3+

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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+

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 The spectrochemical series

•For a given ligand, the color depends on the oxidation state of the metal ion.

•For a given metal ion, the color depends on the ligand.

I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO

WEAKER FIELD STRONGER FIELD

SMALLER Δ LARGER Δ

LONGER λ SHORTER λ

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High-spin and low-spin complex ions of Mn2+

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Orbital occupancy for high- and low-spin complexes of d4 through d7 metal ions

high spin: low spin: high spin: low spin:

weak-field strong-field weak-field strong-field
ligand ligand ligand ligand

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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

λ / nm (wavelength) −
ν / 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, Δoct or Δtet 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
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

λ / nm

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

ES ES

eg eg
hν
GS Δo GS

t2g t2g

complex in electronic d-d transition complex in electronic

Ground State (GS) excited state (ES)

[Ti(OH2)6]3+ λmax = 510 nm Δo is ∴ 243 kJ mol-1

20 300 cm-1

An electron changes orbital; the ion changes energy state

 Limitations of ligand field theory

[Ni(OH2)6]2+ = d8 ion 3 absorption bands

2+ A
eg

Ni

t2g

25 000 15 000
−
ν / cm-1

LFT assumes there is no inter-electron repulsion

Repulsion between electrons in d-orbitals has an effect on the energy of the whole ion
d2 ion Electron-electron repulsion

eg eg
z2 x2-y2 z2 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
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 4A

2g
d5 (high spin) 6A
1g
d6 (low spin) 1A
1g
d8 3A
2g

2B
1g A
2E
g [Ti(H2O)6]3+, d1
2A
1g

2T
2g

ν- / cm-1
10 000 20 000 30 000
 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 ε 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

Tanabe-Sugano diagram for d2 ions 10

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

ε
5

E/B
30 000 20 000 10 000
−
ν / cm-1

ν1 = 17 800 cm-1 visible

ν2 = 25 700 cm-1 visible
ν3 = obscured by CT transition in UV

25 700 = 1.44 Δ/B = 32

17 800

ν3 = 2.1ν1 = 2.1 x 17 800

∴ ν3 = 37 000 cm-1
Δ/B = 32
 E/B

ν1 = 17 800 cm-1
ν2 = 25 700 cm-1

ν2
E/B = 43 cm-1

E/B = 30 cm-1 ν1

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

B = 600 cm-1
Δo / B = 32
Δo = 19 200 cm-1 Δ/B = 32
Tanabe-Sugano diagram for d3 ions
ν1 = 17 400 cm-1 visible
[Cr(H2O)6]3+: Three spin allowed transitions ν2 = 24 500 cm-1 visible

E/B ν3 = obscured by CT transition

24 500 = 1.41
17 400

Δ/B = 24

ν3 = 2.1ν1 = 2.1 x 17 400

∴ ν3 = 36 500 cm-1

Δ/B = 24
 Calculating ν3 ν1 = 17 400 cm-1
ν2 = 24 500 cm-1

E/B
When ν1 = E =17 400 cm-1
E/B = 24
so B = 725 cm-1

When ν2 = E =24 500 cm-1

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

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

Δ/B = 24
 d5 Tanabe-Sugano diagrams
4T
2g

2A
1g
E/B
4T
4E
1g All terms included
g
4T
2g Ground state assigned to E = 0
4A 4
1g, E
2A
Higher levels drawn relative to GS
1g
2T
1g Energy in terms of B
2T
2g High-spin and low-spin configurations
2E
g

4A 2
2g, T1g
Critical value of Δ

4T
2g

6A
1g
4T
1g

2T
2g

WEAK FIELD Δ/B STRONG FIELD

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
TiBr4 d0 ion orange
TiI4 d0 ion dark brown

[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
Lπ∗
eg*

t2g*

Md
Lπ

Lσ
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