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2.

1 Colours and Magnetism


Many transition metal compounds are coloured
Electrons in partially filled d-orbitals can absorb visible light &
move to d-orbitals with slightly higher energy - more later
(ScIII, TiIV & ZnII are exceptions - filled or empty d-subshell)
ZnSO4.7H2O

K3[Fe(CN)6]
TiO2

Na2CrO4

Ni(NO3)2.6H2O

VOSO42H2O
Sc2O3

CoCl2.6H2O
MnCl2.4H2O
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CuSO4.5H2O
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2.1 Colours and Magnetism


Many transition metal compounds are paramagnetic
Partially filled d-subshell with unpaired electrons (attracted to external
magnetic field - more later)

Diamagnetic all electron


spins paired;
no net
magnetic
moment.

Paramagnetic - unpaired spins.


Magnetic fields are randomly
arranged, unless placed in an
external magnetic field Ferromagnetic

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2.1 Colours and Magnetism


Many transition metal compounds are paramagnetic
Partially filled d-subshell with unpaired electrons (attracted to external
magnetic field - more later)

Diamagnetic all electron


spins paired;
no net
magnetic
moment.

Paramagnetic - unpaired spins.


Magnetic fields are randomly
arranged, unless placed in an
external magnetic field Ferromagnetic

Main group ionic compounds are colourless & diamagnetic


Electrons are paired. Energy of visible light is not enough to promote
electrons into empty higher orbital levels
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2.2 The Group 6 Elements - a closer look

No obvious increase in reactivity as we descend


the Group (c.f. Main Group elements)

Ionisation Energy
(kJ/mol)

IE increases as we descend TM Groups


metals become less reactive and poorer
reducing agents
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2.2 The Group 6 Elements - Chromium (Cr)


Chroma - from Greek for colour
Ground state configuration 4s1 3d5
- common oxidation states: +2, +3 and +6
Stainless steel contains up to 18% Cr (slows oxidation).
Coloured compounds (Cr3+ violet; Ruby Al2O3:Cr).

Wood Preservative:
Copper Chromium Arsenate
- contains CrAsO4 and Cr(OH)3
npic.orst.edu/hottopic/cca/index.html

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2.2 The Group 6 Elements - Chromium (Cr)


Cr metal and Cr2+ are strong reducing agents.
Cr + 2H+ (aq)
4Cr2+ + O2 + 4H+ (aq)

Cr2+ (aq)

H2(g)

4Cr3+ (aq) + 2H2O(l)

E0 = 1.66V

In acid, Cr(VI) oxo-anions are strong oxidising agents


Cr2O72- (aq) + 14H+ (aq) + 6e-

2Cr3+ (aq) + 7H2O(l) E0 = 1.33V

Oxidized by HCl
or H2SO4 to form
blue Cr2+ ion.

Cr2+ oxidized by O2
in air to form green
Cr3+.

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2.2 The Group 6 Elements - Chromium (Cr)


Oxides:
non-metallic character & acidity increase with oxidation state.

CrO is basic & ionic - dissolves in acid

Cr2+

Cr2O3 is amphoteric;
Cr2O3 + 6 H+ (aq)

2 Cr3+ (aq) + 3 H2O(l)

Cr2O3 + 3 H2O + 2 OH- (aq)

2 Cr(OH)4- (aq)

CrO3 is deep red , covalent and acidic.


CrO3 (s) + H2O

H2CrO4 (aq)

1/2 H2Cr2O7 (aq) + 1/2H2O


present in strong acids

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2.2 The Group 6 Elements - Chromium (Cr)


CrO3 is a strong reducing agent (Cr is highly oxidised).

YouTube: Chromium Trioxide (FAIL)


http://www.youtube.com/watch?v=_HvYJQ5Bofk

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2.2 The Group 6 Elements - Chromium Cr(VI)


for your interest..

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2.2 The Group 6 Elements - Chromium (Cr)


Cr found in +6
state as in CrO42

..and the strong


oxidizer Cr2O72.

Tetrahedral Cr(VI)
centres
H2CrO4 (aq) + 2OH- (aq)

CrO42- (aq) + 2H2O (l)

2 CrO42- (aq) + 2H+ (aq)

2 Cr2O72- (aq) + H2O (l)


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End of Lecture 3 (Week 8/1)

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Learning Objectives

Understand and apply knowledge of;

formation of coordination complexes and their


properties

what a Ligand is

composition of coordination complexes

geometry of complexes

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2.3 Coordination Compounds


A coordination compound (Complex) consists of a
central cation (metal ion) bonded to molecules or
anions (called Ligands).

Counter ions may be present to maintain charge balance.


2+

3+
H3N

Co

H3N

NH3
NH3

NH3

NH3

NH3
3Cl-

H3N

Co

H3N

Cl
NH3
NH3

Cl

2Cl-

H3N

Co

H3N

NH3

Cl-

NH3
Cl

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2.3 Coordination Compounds


A complex may dissociate into anions and cations in
solution - can behave as an electrolyte.
Ligands remain attached to the metal ion!

In water, [Co(NH3)6]Cl3 dissociates into [Co(NH3)6]3+ and 3Cl- ions


Solutions conduct electricity.
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2.4 Lets meet Alfred Werner (1866-1919)


Father of Coordination Chemistry
Awarded Nobel Prize for Chemistry in
1913.
(Further reading: http://nobelprize.org/)

Introduced the concept of coordination


number, and explained the existence of
optically active metal complex isomers.
Made hundreds of new compounds and studied their
configurations - over 2500 compounds in his collection are
still held at the University of Zurich!
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2.4 Alfred Werner Werners Data


Measured the physical properties of various complexes
Traditional
Formula

Total
Ions

Free
Cl-

Modern
Formula

Charge of
Complex Ion

CoCl3 6 NH3

[Co(NH3)6]Cl3

3+

CoCl3 5 NH3

[Co(NH3)5Cl]Cl2

2+

CoCl3 4 NH3

[Co(NH3)4Cl2]Cl

1+

CoCl3 3 NH3

[Co(NH3)3Cl3]

0
(See previous table)

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2.4 Alfred Werner Werners Paper

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2.4 Alfred Werner Werners Insights


Realised CoCl3(NH3)6 was not a simple ionic salt but
a complex cation, [Co(NH3)6]Cl3
Complex was ionic
Oxidation state was Co(III)
Molecule was octahedral
6 NH3 ammonia ligands (CN=6)
Cl- not coordinated but ionic counter ions

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2.4 Alfred Werner Werners Insights

Approach correctly predicts there


would be two forms of CoCl3 4 NH3.
The formula would be written
[Co(NH3)4Cl2]Cl.
One form has the two chlorines next to
each other.
The other has them opposite each
other.
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2.5 Geometries of Coordination Complexes


Kepert theory: complex shapes depend on repulsion of
ligands
Geometry - depends on coordination
number & nature of ligand.
Generally follow VSEPR theory - square
planar geometry an exception.
Linear 2 donor atoms
Trigonal planar - 3 donor atoms
Tetrahedral - 4 donor atoms
Exception for some 4-coordinate
complexes which are square
planar
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2.5 Geometries of Coordination Complexes


Kepert theory: complex shapes depend on repulsion of
ligands

Trigonal bipyramidal or
square-based pyramidal - 5
donor atoms
Octahedral - 6 donor atoms

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2.6 Components of Coordination Compounds


Cl

Consider the complex:


Ligands - molecules/ions attached to
metal ion, NH3 & Cl-.

H3N
H3N

NH3
NH3

NO3.H2O

Cl

Donor atoms - atoms bonded to metal ion - must have at


least one lone pair of electrons; N on NH3 & Cl-; not N, O on
NO3-.
Overall charge = +1
Oxidation state = charge - (charge on ligands) = +1-(-2)=
+3
Counter-ion - balances charge on complex - nitrate (NO3-).
Hydrate - water present in crystal lattice.
Coordination number = number of donor atoms = 6.
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2.7 - Summary of Coordination Complexes


A Complex consists of a central cation (Metal ion)
bonded to molecules or anions (called Ligands).
d-block elements in low oxidation states
Counter ions may be present to balance charge.
A complex may dissociate into cations and anions in
solution - electrolyte.
Ligands remain attached to the metal ion

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2.7 - Summary of Coordination Complexes


Molecules/ions act as ligands, are Lewis bases and
coordinate to the metal ion
Since the ligand provides a lone pair to the metal the
bond is often indicated by an arrow.
The number of ligands bound to the metal is the
coordination number (CN)
In a coordination complex, the coordination number of the
metal centre is not related to the oxidation state!
2+

NH3
H3N
H3N

Ni
NH3

NH3
NH3

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Knowledge Checklist
Electronic configurations: d-block
The group number = total number of valence electrons
Approx. filling order: 1s<2s<2p<3s<3p<4s<3d<4p..
Orbital energy can change for some elements
eg. Cu is [Ar]4s13d10, not [Ar]4s23d9

Can you name the 3d elements?


Do you know the stable oxidations states?

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Knowledge Checklist
The d-orbitals, energy and directionality

Recall: principle quantum number, n = 3 l = 0, 1, 2


Hence, ml = +2,+1,0,-1,-2.
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Knowledge Checklist

Note: for the d-metal ions, the energy of the 3d orbital lies
below the 4s hence the electronic configuration is Fe2+ [Ar]3d6
not [Ar]4s23d4
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End of Lecture 4 (Week 8/2)

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