Lecture Slides 1

B17CB
Chemical Reactivity
Inorganic Chemistry
Topic 1
Transition-metal Chemistry
Version Aug 2013 © Heriot-Watt University 1

Transition Metal Chemistry

Why Study Transition Metals?
• Fascinating Chemistry
• Extraordinary range of structures
• Show variable oxidation states
• Many used as catalysts in huge range of

reactions
• e.g. Fe in ammonia synthesis,
• V2O5 in SO3 synthesis

Extraordinarily beautiful
range of colours

This, I hope is
Quantum Numbers revision!
n l ml no. name
of orbitals of orbitals
1 0 0 1 1s
2 0 0 1 2s
1 1, 0, -1 3 2px,2py,2pz
3 0 0 1 3s
1 1, 0, -1 3 3px, 3py, 3pz
2 2, 1, 0, -1, -2 5 see later
d-orbitals
When l = 2, there are 5 possible values of ml
So any set of d-orbitals contains 5 different orbitals
dxy, dxz, dyz, dx2-y2, dz2
Each orbital may accommodate up to 2 electrons

- any period of Transition Metals is 10 members long
BOTH the SHAPE AND ORIENTATION in space

of these orbitals are very important
Transition Metal Series exist for 4th, 5th 6th and
now 7th period of the Periodic Table
In this set of lectures we will focus almost entirely

on 4th period elements (Sc – Zn).
• most commonly found

• most chemistry known
It is ESSENTIAL that you know this series in the

correct order
Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn

Elements e configurations

Elements e configurations
We know chemistry of an element
depends crucially on its VALENCE
ELECTRON CONFIGURATION
Filling of Orbitals (see previous slide)
1. For the elements, 4s orbital tends to fill before 3d
Consequence – K is 4s1, Ca is 4s2, Sc is 4s2 3d1 etc
Why? For the ELEMENT, 4s orbital is lower energy

than 3d, and electrons fill lower energy states first
(Aufbau principle)
2. Two ‘anomalies’ exist in orbital filling – Cr and Cu.

These elements have only one 4s electron – the ‘other
4s electron’ is in the 3d set of orbitals
-produces a half-filled (Cr) or filled (Cu) 3d subshell
4s1 3d5 4s1 3d10
Common observation in chemistry
- half-filled or filled orbital set has added stability

-(arises from alignment of parallel electron spins
- and is also the basis for Hund’s rule)
BUT this is NOT a major energy factor
However, with Cr and Cu, because the 4s and 3d

orbitals are close in energy, additional stability of the
half-filled and filled d-orbitals makes the observed
electron configurations (4s1 3d5 and 4s1 3d10) a bit
more stable than 4s2 3d4 and 4s2 3d9

First THREE ionization energies
First 3 Ionization Energies 1stSeries
of First Transition Transition Series
4500
4000
3500
3000
I.E./kJmol-1
2500 1st IE
2nd IE
2000 3rd IE
1500
1000
500
0
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Element

Formation of Transition Metal Ions
Notes on Ionization Energies – consider IE Graph
1. 1st IE is rather small – (ca. 650 to 900 kJ mol-1)

only slight increase L→R, as nuclear charge ↑
TMs are easy to oxidise
- always loss of a 4s electron
2.Electrons in a spherical s orbital experience little

change in nuclear charge across series => s
electrons are well ‘screened’ by inner electrons =>
easy to remove s electrons.
3.2nd IE also quite small (ca. 1300 to 2000 kJmol-1)

=> TMs readily form 2+ ions
4. Values for Cr and Cu are higher than expected
from trend → this is for removal of a 3d electron
5. 3rd IE is quite large (ca. 2500 to 4000 kJ mol-1)

– big variation across series.
For ALL TMs, this is removal of a 3d electron
=> 3d electrons more strongly influenced by
nuclear charge → this increases across series.
=> increasingly difficult to produce 3+ ions across
series
Why is 3rd IE curve not smooth? i.e. why is it easier

to oxidise Fe2+ than Mn2+, despite its larger nuclear
charge?
Look at electron distribution:
Mn2+ ↑ ↑ ↑ ↑ ↑
Fe2+ ↑↓ ↑ ↑ ↑ ↑
Mn2+ - all d orbitals singly occupied

Fe2+ has 2 e in same orbital → greater e/e
repulsion → unfavourable
Easier to remove e from Fe2+ than Mn2+
Relatively small IE values between different

oxidation states, and variation across table allows
TMs to show variable oxidation states across series.
CHARACTERISTIC PROPERTY OF TMs
VERY IMPORTANT to get correct d-electron count for
ANY TM ion
i.e. I mean ABSOLUTELY ESSENTIAL
Elements show non-systematic behaviour for Cr and

Cu. Sc2+ 4s0 3d1
BUT note Ti2+ 4s0 3d2
V2+ 4s0 3d3
Cr2+ 4s0 3d4
Mn2+ 4s0 3d5
Fe2+ 4s0 3d6
Co2+ 4s0 3d7 Filling in
Ni2+ 4s0 3d8 sequence
Cu2+ 4s0 3d9
for 2+ ions
Zn2+ 4s0 3d10
Transition metal oxidation states
[ T p.515 ]
Most important states highlighted

Note only trends in this table
1. For Sc→Mn, maximum oxidation state = total

no. of valence e
2. Highest oxidation states of V, Cr and Mn are
stabilized by covalent bond formation BUT even
so are strongly oxidising species
e.g MnO4- (Mn 7+) CrO42- (Cr 6+)
3. After Mn the max. common oxidation state is 3+
Why? Nuclear charge ↑ L to R across table.

Increasingly difficult to oxidise metals to states higher
than 3+.
N.B. in oxidation - 4s electrons lost first,
BEFORE any removal of 3d electrons
Why?
While in elements, 4s is lower in energy than 3d,

once we form compounds and ions, 3d orbitals
are lowered in energy more than 4s.
Because of different shapes, d orbitals are more

affected than s by changing nuclear charge.
Result
Once we form ions, 3d electrons are lower in
energy than 4s
- system continues to follow aufbau principle.
Shapes of d-orbitals

d-orbitals – Note the orientation in space
Another view of
d-orbitals
This view
emphasises e-
density
distribution with
respect to
orbital boundary
surface
N.B. darker dots
= more electron
probability

Shapes of d-orbitals

Shading of d-orbitals
Wave
unshaded
Amplitude
shaded

Notes on d-orbitals [Text p125]
1. In the unperturbed atom, or ion, all 5 of the d-

orbitals are exactly the same energy –
DEGENERATE
2. Three of the d-orbitals have their lobes pointing
BETWEEN the x, y and z axes in their name.
dxy dxz dyz

3. TWO of the orbitals have their lobes pointing
ALONG axes in their name.
dx2-y2 dz2
Chemistry of Transition Metals
a)Simple species – consist of cations and anions
e.g FeF2, CuSO4, NiS, Cr2O3
Chemistry based on infinite lattice solid-state
structures.
b) Complex species [Text p520]
Chemistry based on formation of
DONOR-ACCEPTOR BONDS
e.g. Fe2+(aq) + NH3 (aq)  [Fe ←:NH3 ] (aq)
Fe-N is a CO-ORDINATE BOND
– ‘CO-ORDINATION
Version Aug 2013 CHEMISTRY’
© Heriot-Watt University 27
n+ n+
M + L M L
Co-ordinate Covalent Bond
Example

Definitions in Co-ordination Chemistry
1. ‘Co-ordination Chemistry’ – describes the
formation of ‘complexes’ – compounds
containing bonds between an electron pair
donor and electron pair acceptor
2. ‘Complex’ – metal ion bonded to several
anions or molecules – ‘ligands’
3. ‘Ligand’ – ion or molecule that donates at
least one electron pair to a metal ion to form a
DATIVE COVALENT BOND
4. ‘First Co-ordination Sphere’ – ligands
bonded directly to the metal ion
5. ‘Co-ordination number’ – number of donor
atoms in the first co-ordination sphere.
e.g. 1 FeCl3.6H2O
Fe3+ - SIX water molecules bonded to Fe3+ by
lone pair on each O atom
First co-ordination sphere  6 H2O molecules
Co-ordination number  SIX
Write as [Fe(H2O)6]Cl3 Square brackets show
metal +1st Co-ord sphere
NB Cl- ions NOT bonded directly to metal ion

but needed to balance charge
e.g. 2 Pt(NH3)2Cl2
Pt2+ 2 ammonia molecules and 2 Cl- ions bound
via lone pairs of electrons
First co-ordination sphere
 Pt2+ has co-ordination number FOUR
[Pt(NH3)2Cl2]
No groups outside first co-ordination sphere

Charge on a complex is sum of charges of
constituent parts.
Complexes can be CATIONIC, NEUTRAL or
ANIONIC
e.g.1 K3 [Fe(CN)6]
Each K is 1+ (Gp1 species)  [Fe(CN)6]3-
Cyanide ion is CN- (x6)  6-
So Fe has to be 3+ (to balance charge)

e.g. 2 [Co(NH3)5Cl]Cl2
Each Cl is Cl- (Gp 17 ) ; ammonia neutral molecule
Cobalt is 3+ and complex ion is [Co(NH3)5Cl]2+
e.g. 3 [Ni(CO)4]
Carbon monoxide is neutral molecule
Ni is uncharged
Complex [Ni(CO)4] is a neutral species

Extreme versatility in structure of complexes leads
to fascinating chemistry
e.g. consider a family of Pt(4+)/NH3/Cl-

complexes of apparently similar formula

Empirical Conduct No. No. Formula
Formula (ohm-1) Ions Cl-
PtCl4.6NH3 523 5 4 [Pt(NH3)6]Cl4

PtCl4.5NH3 404 4 3 [Pt(NH3)5Cl]Cl3
PtCl4.4NH3 229 3 2 [Pt(NH3)4Cl2]Cl2

[Pt(NH3)3Cl3]Cl
PtCl4.3NH3 97 2 1
[Pt(NH3)2Cl4]
PtCl4.2NH3 0 0 0
K[Pt(NH3)Cl5]
PtCl4.NH3.KCl 109 2 0
PtCl4.2KCl 256 3 0 K2[PtCl6]
Co-ordination Number - Complex Ion Geometry
[Text p 524]
COMMON Co-ordination numbers
6 5 4 2
MOST COMMON BY FAR
6 Co-ordinate  ‘Octahedral Geometry’ Oh

Ligands exist at corners of a regular octahedron
(metal at centre)

6-co-ordinate geometry – based on Octahedron
[Cu(H2O)6]2+ ion
5 Co-ordinate Geometry - much less common
TWO geometries found

- Trigonal Bipyramidal or Square-pyramidal
e.g.

4-co-ordinate geometry – either
Tetrahedron or Square Plane
M
M
e.g. [Zn(H2O)42+] e.g. [Pt(NH3)2Cl2]

TWO Co-ordinate - Linear (rather unusual)
[H3N-Ag-NH3]+ ion
[NC-Au-CN]- ion

Types of Ligand [Text p 516]
Classified by number of donor atoms
Monodentate – one atom binds to metal ion
(literally ‘one-toothed’)
e.g. H2O NH3 F- PEt3
Bidentate – two donor atoms on each ligand

e.g. 1,2-diaminoethane – both N atoms can
bind to metal centre  ‘chelate’ structure
H2C CH2
H2N NH2 Abbreviated as ‘en’

Complex example
e.g. [Co(en)3]3+
3+
NH2
H2N NH2
Co
H2N NH2
NH2
Also oxalate ion, [C2O4]2- bonds via two O atoms

O O
C C
O O
Tridentate
Tetradentate
Originally studied as
pigments by Scottish
Dyes Ltd, Grangemouth
Nickel(II)
Macrocyclic
Complex
-made at Heriot-
Watt as part of
research work on
Bioinorganic
Chemistry

Hexadentate
Ethylenediamine tetra-acetate ion (EDTA4-)
O
-
O O
-
N O
O N - -wraps
around
O O
metal ion
-
O
[Co(EDTA)- ] complex

Crude Schematic of O2 binding in Haemoglobin
sub-unit
O2 molecule
Fe2+ ion
Isomerism in TM Complexes [Text p526]
1. Geometric Isomerism
A. cis or trans - requires TWO identical groups
in first co-ordination sphere (Oh or square plane)
e.g. [Co(NH3)4Cl2]+ Cl- (i.e. 4 NH3 and 2 Cl-

ligands, plus Cl- ion to balance charge
Cis Cl-Co-Cl angle 90o Trans Cl-Co-Cl angle 180o

Also found in square planar complexes
- can get 90o and 180o angles
e.g.
Cl NH3 Cl NH3
Pt Pt
Cl NH3 H3N Cl
Cis isomer Trans isomer

B. Fac or Mer – requires 6 co-ord. complex with
3 identical monodentate ligands
e.g. Fac and Mer isomers of [Co(NH3)3Cl3]
Fac isomer – Mer isomer –
Cl ions cap a face

- Cl- ions occupy a
meridian
Cl- ions at corners Cl- ions all in same
of equilateral plane as metal
triangle
=> mer isomer
=> fac isomer

Linkage Isomers [Text p526]
-Found with ligands with more than one type of
possible donor atom
-e.g. N bonded and O bonded NO compounds

e.g. Thiocyanate ligand, SCN-
Both S and N atoms can bind to metal

- AMBIDENTATE ligand
S C N

Co-ordination Sphere Isomerism Example
Found where more possible donor groups than

acceptor sites

e.g. species with empirical formula CrCl3.6H2O
3+
H2O
H2O OH2
Find [Cr(H2O)6]Cl3 Cr
H2O OH2
OH2
2+
H2O
H2O OH2
[Cr(H2O)5Cl]Cl2.H2O H2O
Cr
OH2
Cl
+ +
OH2 Cl
H2O OH2 H2O OH2
Cr
[Cr(H2O)4Cl2]Cl.2H2O H2O
Cr
Cl H2O OH2
Cl Cl
Cis + trans possible
Optical Isomers
– mirror image cannot be superimposed on original
Compound is ‘CHIRAL’
Original and image are ‘ENANTIOMERS’
Enantiomers rotates plane of
polarized light

Optical isomers of 6 co-ordinate complexes
e.g. tris-oxalato ferrate ion [Text p526]
Object Mirror image

- will not superimpose => enantiomers
e.g. [Co(en)2Cl2]+

Classification of Isomers
ISOMERS
Structural Isomers Stereoisomers

(Different Bonds to Metal) (Same Bonds but
Different Arrangement)
Co-ordination Linkage Geometric Optical

Sphere Isomers Isomers Isomers Isomers

Colour of Transition Metal Complexes
Crystal Field Theory and d-orbital Splitting
Consider Oh
Ligands
move to Mn+
along x,y,z
axes
Ligand e-
repel Mn+ e-
Repulsion unfavourable -
raises energy of d-orbitals
Interaction of d-orbitals with ligand electrons
Repulsion greater where e- get closer –

dx2-y2 and dz2 show greater repulsion than dxy, dxz and
dyz
- In complexes, d-orbitals no longer degenerate but
split into TWO sets => ‘d-orbital splitting’
Model of Ligands and dxz orbital

Splitting of d-orbitals

dx2-y2 and dz2 point directly at ligands – greater e-/e-
repulsion – raised higher in energy
dxy, dxz and dyz point between axes – less e-/e-
repulsion – not so high in energy
d-orbitals split into TWO sets separated in energy
by ‘SPLITTING ENERGY’ – symbol o
eg
o
t2g
The value of o varies with the ligands

- Usually (by chance) similar energy to visible light
Electromagnetic Spectrum
– highlighting Visible region
Low Energy High Energy End

End

e.g. [Ti(H2O)6]3+ ion - d1 [Text p536]
eg
o
t2g
e- absorbs energy (value o) moves from t2g to eg

Energy is in visible spectrum – photon of GREEN light.
BLUE and RED light NOT absorbed - ion appears

PURPLE
Colour of Complexes
Colour opposite any colour

on wheel 
‘complementary colour’
If substance absorbs a
colour from white light,
observed colour of reflected
or transmitted light is
complementary colour
e.g. Absorb blue/green –

appears orange
[Ti(H2O)6]3+ spectrum
eg
t2g
e- absorbs photon to
move from t2g to eg

But o varies with the ligands – so colour of
complexes depends on the ligands bonded to
the metal ion
Note – to see colour

Must have at least 1 e- in t2g orbitals
Must have a vacancy in eg orbitals
e.g. [Ti(H2O)6]3+ d1 is coloured
But [Sc(H2O)6]3+ d0 and [Zn(H2O)6]2+ d10 are not

Spectrochemical Series [Text p533]
List of ligands in increasing size of o
e.g. for selected ligands

F- < H2O < NH3 < NH2-CH2CH2-NH2 < CN-
Small o Large o
‘weak field’ ‘strong field’

Consider Co3+ complexes – d6 ion
[CoF6]3- [Co(NH3)6]3+ [Co(CN)6]3-
eg
eg
eg
o
o o
t2g t2g t2g
F- weak CN- strong

field ligand field ligand
Magnetic Properties of TM Complexes
‘High Spin’ and ‘Low Spin’ complexes [Text p533]
Some electronic configurations can be found in

more than one arrangement
e.g. Ni3+ 4s03d7
o
o
Max. no. of Min. no. of

unpaired e- unpaired e-
To place TWO electrons in same orbital, energy is
needed to PAIR ELECTRONS
- this is called the PAIRING ENERGY, P
To place e- in an eg rather than a t2g orbital, require

to input energy o
Whether complex is ‘high spin’ or ‘low spin’

depends on relative size of P and o
-system will always choose LOWEST ENERGY
If o < P → get HIGH SPIN – Maximum unpaired e-

If o > P → get LOW SPIN – Minimum unpaired e-
Vocabulary
Species with no unpaired electrons –

DIAMAGNETIC
Species with at least one unpaired

electron –
PARAMAGNETIC

Only get possibility of ‘high spin’ and ‘low spin’
configurations for d4 to d7 [Text p 534]
Why?
• There is no ambiguity about the way in which the

orbitals are filled for d1, d2 and d3
• Value of o does not matter, and no P involved
•Version
Configurations
Aug 2013
obey aufbau principle
© Heriot-Watt University 76
For d8, d9 and d10
- no ambiguity about the way in which the orbitals
are filled either
t2g set completely full
o not relevant

However for d4, d5, d6, d7 - relative size of o and
P DOES matter
o > P o < P
Cost less Cost less

energy to energy to
PAIR e- place e- in
than place eg orb than
in eg orb to PAIR

So for
weak field ligands (small o) give high spin

complexes
e.g. F-, Br-, Cl-
strong field ligands (large o) give low spin

complexes
e.g. CN-, CO

The magnetic properties of transition
metal complexes
•Paramagnetic compounds contain
unpaired electrons
•Number of unpaired electrons determines
the magnitude of compounds response to
a magnetic field
•The response of a compound to a
magnetic field can be measured accurately
•‘Magnetic moment’ measure in Bohr
Magnetons (B.M.)

The ‘ spin-only’ formula
Magnetic properties of transition metal complexes
can be estimated from no. unpaired e-
 =  n (n+2) B.M.
where n is no. of unpaired electrons in complex
Estimated values of 
No. unpaired e (spin only) /B.M.
1 1.73
2 2.83
3 3.87
4 4.90
5 5.92
The Gouy Method - gives experimental value of 
Weight of sample measured in presence and absence of

magnetic field
Apparent increase in weight → sample paramagnetic
Apparent decrease in weight → sample diamagnetic
Increase in weight proportional to  value
Gouy method → find experimental value of .

Use to find no. of unpaired e- in complex –
compare experimental value with estimated value
e.g. Cr2+ complexes → 3d4 ion
[Cr(OH2)6]2+ measured  = 4.9 B.M.
-closest ‘spin-only value’ = 4.90 B.M. (of course!)
=> Complex has 4 unpaired e- → high-spin
[Cr(CN)6]4- measured  = 2.8 BM

-closest ‘spin-only’ value = 2.83 BM
=> Complex
Version Aug 2013 has 2 unpaired
© Heriot-Watt University→
e -
low-spin 83
Modern Method

Effect of a Magnet on a Paramagnetic Solid

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B17CB

Version Aug 2013 © Heriot-Watt University 1

Version Aug 2013 © Heriot-Watt University 2

• Extraordinary range of structures

• Show variable oxidation states

• Many used as catalysts in huge range of

Version Aug 2013 © Heriot-Watt University 3

Version Aug 2013 © Heriot-Watt University 4

So any set of d-orbitals contains 5 different orbitals

dxy, dxz, dyz, dx2-y2, dz2

Each orbital may accommodate up to 2 electrons

BOTH the SHAPE AND ORIENTATION in space

In this set of lectures we will focus almost entirely

• most commonly found

It is ESSENTIAL that you know this series in the

Version Aug 2013 © Heriot-Watt University 8

Version Aug 2013 © Heriot-Watt University 9

Why? For the ELEMENT, 4s orbital is lower energy

2. Two ‘anomalies’ exist in orbital filling – Cr and Cu.

- half-filled or filled orbital set has added stability

BUT this is NOT a major energy factor

However, with Cr and Cu, because the 4s and 3d

Version Aug 2013 © Heriot-Watt University 12

Version Aug 2013 © Heriot-Watt University 13

1. 1st IE is rather small – (ca. 650 to 900 kJ mol-1)

2.Electrons in a spherical s orbital experience little

3.2nd IE also quite small (ca. 1300 to 2000 kJmol-1)

5. 3rd IE is quite large (ca. 2500 to 4000 kJ mol-1)

Why is 3rd IE curve not smooth? i.e. why is it easier

Mn2+ - all d orbitals singly occupied

Relatively small IE values between different

Elements show non-systematic behaviour for Cr and

Most important states highlighted

Version Aug 2013 © Heriot-Watt University 18

1. For Sc→Mn, maximum oxidation state = total

Why? Nuclear charge ↑ L to R across table.

While in elements, 4s is lower in energy than 3d,

Because of different shapes, d orbitals are more

Version Aug 2013 © Heriot-Watt University 21

Version Aug 2013 © Heriot-Watt University 23

Version Aug 2013 © Heriot-Watt University 24

Version Aug 2013 © Heriot-Watt University 25

1. In the unperturbed atom, or ion, all 5 of the d-

dxy dxz dyz

Version Aug 2013 © Heriot-Watt University 28

NB Cl- ions NOT bonded directly to metal ion

No groups outside first co-ordination sphere

Version Aug 2013 © Heriot-Watt University 31

Version Aug 2013 © Heriot-Watt University 32

Version Aug 2013 © Heriot-Watt University 33

e.g. consider a family of Pt(4+)/NH3/Cl-

Version Aug 2013 © Heriot-Watt University 34

PtCl4.6NH3 523 5 4 [Pt(NH3)6]Cl4

PtCl4.4NH3 229 3 2 [Pt(NH3)4Cl2]Cl2

6 Co-ordinate  ‘Octahedral Geometry’ Oh

Version Aug 2013 © Heriot-Watt University 36

TWO geometries found

Version Aug 2013 © Heriot-Watt University 38

e.g. [Zn(H2O)42+] e.g. [Pt(NH3)2Cl2]

Version Aug 2013 © Heriot-Watt University 40

Bidentate – two donor atoms on each ligand

H2N NH2 Abbreviated as ‘en’

Also oxalate ion, [C2O4]2- bonds via two O atoms

Version Aug 2013 © Heriot-Watt University 44