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TRANSITION ELEMENTS

Objectives Objectives
Write valence electron configurations for transition-metal atoms and
ions.
Identify the ligands and their donor atoms. Determine coordination y g
number and oxidation state of the metal, and the charge on any
complex ion.
Write formulas of coordination complexes and Name coordination p
compounds.
Identify types of isomers, and draw structures of isomers
Give a valence bond theory description of a coordination complex and Give a valence bond theory description of a coordination complex and
show the number of unpaired electrons and the hybrid orbitals used by
the metal ion.
Give a crystal field theory description of a coordination complex and Give a crystal field theory description of a coordination complex and
show the number of unpaired electrons.
Transition elements Transition elements
W f t iti l t i d lif We use many of transition elements in everyday life
Wiring: copper (Cu)
Pipe: Iron (Fe) copper (Cu) Pipe: Iron (Fe), copper (Cu)
Jewelry: Gold (Au), Silver (Ag), Platinum (Pt),
Light bulb: Tungsten (W)
Compounds of the transition elements are also used in many applications
Silver iodide (AgI) is a component of photographic film
Zirconium silicate (ZrSiO
4
) is used in artificial gemstones
Chromium (IV) oxide (CrO
2
) is used in magnetic recording tape
C l f i (F ) i f d i h l bi i bl d Complex of iron (Fe) is found in hemoglobin in your blood
Colour of transition metal complexes Colour of transition metal complexes
Ruby
Corundum
S hi
Al
2
O
3
with Cr
3+
impurities
Sapphire
Corundum
Al
2
O
3
with Fe
2+
and Ti
4+
impurities impurities
Emerald
Beryl
AlSiO
3
containing Be with Cr
3+
impurities
Transition Elements Transition Elements
Lanthanide series
Actinide series
Transition elements Transition elements
Metallic elements that have an incompletely filled
d subshells or easily become ions with incompletely y p y
filled d subshells.
Examples Examples
[ ]
[ ]
6 2
26
14 9 1
Iron Fe Ar 3d 4s
[ ]
14 9 1
78
Platinum Pt Xe 4f 5d 6s
Inner transition elements Inner transition elements
Metallic elements that have partially filled f
subshells.
Examples
[ ]
1 1 2
Cerium Ce Xe 4f 5d 6s
[ ]
[ ]
58
2 1 2
91
Cerium Ce Xe 4f 5d 6s
Protactinium Pa Rn 5f 6d 7s
[ ]
91
inner transition elements are called f-block elements
f f f The first row of f-block elements are called Lanthanide series
The second row of f-block elements are called Actinide series
Main group and Transition elements Main group and Transition elements
Main group elements Transition elements
Metal and non metal
Low melting and
All metal
High melting and g
boiling points
Compounds
g g
boiling points
Compounds Compounds
Colourless
Di ti
Compounds
Colourful
P ti Diamagnetic
Single oxidation state
Paramagnetic
Several oxidation states
Fi r st t r ansi t i on el ement s : 4
t h
per i od el ement s Fi r st t r ansi t i on el ement s : 4 per i od el ement s
Scandium Sc Iron Fe
Titanium Ti Cobalt Co
Vanadium V Nickel Ni
Chromium Cr Copper Cu
Manganese Mn Zinc Zn Manganese Mn Zinc Zn
Properties of the First transition
elements
Electron configuration Electron configuration
F t iti l t l t b i t fill th 3d bit l For transition elements, electron begins to fill the 3d orbital
[ ]
2 1
Sc Ar 4s 3d
[ ]
2 2
Ti Ar 4s 3d
[ ]
2 3
V Ar 4s 3d
Val enc e
el ec t r ons
Electron configuration Electron configuration
Sc Ti V Cr Mn Fe Co Ni Cu Zn
M 3d
1
3d
2
3d
3
3d
5
3d
5
3d
6
3d
7
3d
8
3d
10
3d
10
M 3d
4s
2
3d
4s
2
3d
4s
2
3d
4s
1
3d
4s
2
3d
4s
2
3d
4s
2
3d
4s
2
3d
4s
1
3d
4s
2
M
2+
3d
1
3d
2
3d
3
3d
4
3d
5
3d
6
M
2+
3d
1
3d
2
3d
3
3d
4
3d
5
3d
6

M
3+
[Ar] 3d
1
3d
2
3d
3
3d
4
3d
5
3d
6
[ ]
There are two exception; Cr and Cu The electron configurations prefer half There are two exception; Cr and Cu. The electron configurations prefer half-
filled and completely-filled 3d orbital
When the metal forms cation, electrons from 4s orbital are removed first and ,
then from 3d orbital.
d
n
ion d ion
When d-block elements form ions, the 4s electrons
are lost first.
The number of electrons left in d subshell will be
used to refer to the type of ion. yp
[ ]
2 2
Ti Ar 4s 3d [ ]
1 5
Cr Ar 4s 3d
[ ]
[ ] [ ]
2 2 2
Ti Ar 4s 3d
Ti Ar 3d not Ar 4s
+
[ ]
[ ]
[ ]
2 4 4
3 3 3
Cr Ar 4s 3d
Cr Ar 3d referred to as d ion
C A 3d f d d i
+
+
2 2
Ti is referred to as d ion
+
[ ]
[ ]
3 3 3
6 0
Cr Ar 3d referred to as d ion
Cr Ar referred to as d ion
+
+
Exercise: Write the electron configuration of the
following ions:
5 3 2 3 2 3 4
V ,Cr ,Mn ,Fe ,Cu ,Sc ,Ti
+ + + + + + +
Melting Points and Boiling Points Melting Points and Boiling Points
As you read across a row of transition elements,
melting points and boiling points increase melting points and boiling points increase,
reaching a maximum at the group VB or VIB
elements after which the melting point decreases elements, after which, the melting point decreases.
These properties depend on the strength of metal
b di hi h i t d d hl th b bonding, which in turn depends roughly on the number
of unpaired electrons.
Atomic radii Atomic radii
Atomic radii Atomic radii
Across the period
Atomic size decreases at first but then remains fairly Atomic size decreases at first but then remains fairly
constant.
The reduction of atomic size across the period is due The reduction of atomic size across the period is due
to an increase in effective nuclear charge
The effective nuclear charges of transition elements g
change very slightly across the period, therefore the
atomic sizes are very similar
Atomic radii Atomic radii
Within the group
Atomic size increases as expected from period 4 to 5
because of the adding outer shell orbital.
There is no size increase from period 5 to 6 because p
of the lanthanide contraction
Lanthanide contraction is the extra shrinkage that g
results from the nuclear charge of the additional 14
elements. This decrease is cancel out the normal
increase between periods.
First ionization energy First ionization energy
First ionization energy gy
Across the period
The first ionization energies increase only slightly
across the period
The d electrons fill inner orbitals, so they The d electrons fill inner orbitals, so they
shield outer electrons from the increasing
nuclear charge much more efficiency nuclear charge much more efficiency
First ionization energy First ionization energy
Within the group
The first ionization energy decreases for elements The first ionization energy decreases for elements
from 4
th
period to 5
th
period but then increases for
elements from 5
th
period to 6
th
period elements from 5 period to 6 period
The first ionization energy for elements increases
because the atomic size changes only slightly but the g y g y
nuclear charge changes much more
Oxidation state Oxidation state
O f One of the most characteristic chemical properties
of the transition metals is the occurrence of multiple
oxidation states
This multiplicity of oxidation states is due to the p y
varying involvement of d electrons in bonding
Since ns and (n-1)d electrons are so close in energy, Since ns and (n 1)d electrons are so close in energy,
transition metals can involve all or most of these
electrons in bondingg
The elements at the beginning (up to Mn) exhibit a highest oxidation state that
corresponds to the loss of all of the electrons in both the s and d orbitals of their p
valence shell.
Transition elements usually exhibit their highest oxidation states
in compounds with very electronegative elements such as
oxygen and fluorine
O i Oxoanions:
( )
3 5
4
Vanadium vanadate ion VO V
+

( )
( )
( )
2 6
4
2 6
Chromium chromate ion CrO Cr
+
+

( )
( )
2 6
2 7
7
4
dichromate ion Cr O Cr
Manganese permanganate ion MnO Mn
+
+


Beyond Mn, the elements are stable with oxidation state of +1,
( )
4
g p g
y , ,
+2 and +3.
The +2 oxidation state is common because ns
2
electrons are
l l easily lost.
Bonding of compounds Bonding of compounds
T iti l t f b th i i b di d Transition elements can form both ionic bonding and
covalent bonding
Ionic bonding is more common in the lower oxidation
state
Covalent bonding is more common in the higher
oxidation state
2
2
4
TiCl Ti ionic solid
TiCl Ti molecular liquid
+
+

4
TiCl Ti molecular liquid
Colour and magnetic properties Co ou a d ag e c p ope es
M t l i th t t i ti ll fill d d bit l ll Metal ions that contain partially filled d orbital usually
form coloured complex ions and also show
paramagnetic property p g p p y
Ions with empty d orbital (d
0
) or filled d orbital (d
10
) form
colourless complexes and show diamagnetic property
3
0
( )
Sc
d
+ 3
3
( )
Cr
d
+ 2
7
( )
Co
d
+ 2
8
( )
Ni
d
+
2
9
( )
Cu
d
+ 2
10
( )
Zn
d
+
( ) d ( ) d ( ) d ( ) d
9
( ) d
10
( ) d
( )
n
2
6
solution of M H O ; M is metal
+


Coordination Compounds
Objectives Objectives
T k h d h d d To know the terms associated with coordination compounds.
To be able to obtain the oxidation state of the central metal
atom in a coordination compound or complex ion atom in a coordination compound or complex ion.
To determine coordination number of a central metal atom
in a coordination compound or complex ion. in a coordination compound or complex ion.
To name a complex ion or coordination compound given its
formula.
To write a formula of a coordination compound or complex
ion given its name.
Coordination compounds Coordination compounds
Coordination compounds are important for three
reasons:
1. Most of the elements in the periodic table are metals,
and almost all metals form complexes
2 Many industrial catalysts are metal complexes and these 2. Many industrial catalysts are metal complexes, and these
catalysts are important as a way to control reactivity
3. Transition-metal complexes are essential in biochemistry p y
a. Hemoglobin, an iron complex that transports oxygen in blood
b. Cytochromes, iron complexes that transfer electrons in cells
C l h f h l f c. Complexes that are components of enzymes, the catalysts for
all biological reactions
Coordination compounds Coordination compounds
Coordination compound : substance that typically
contain at least one complex ion or neutral complex
species
Examples of complex ion [Co(NH
3
)
6
]
3+
3 6
Examples of neutral complex : Pt(NH
3
)
2
Cl
2
and Fe(CO)
5
Complex i
counter ions
on

( )

counter ions
3 3
6
C Co l NH

( )
3 3
6
Complex ion Complex ion
Complex ion consists of a central metal cation
bonded to ligands by coordinate covalent bond
Ligands : molecules or ions that have electrons to
give to metal cation
3+

g
( )
3
3
Co NH
+



( )
3
6
ligand
Co NH



_

Ligand Ligand
Within a ligand the atom attached directly to the
metal through the coordinate covalent bond is
called the donor atom.
N
Donor atom
N
H
H
H
O
H
H
H
H
Ligand or counter ion ? Ligand or counter ion ?
In 1893, Alfred Werner
explained the difference
between the two between the two
compounds above by
representing their p g
dissociation in water.
( ) ( )
3
H O
C Cl C 3Cl
+

( ) ( )
2
H O
3 3 3 (aq)
6 6
(aq)
Co NH Cl Co NH 3Cl
6 li d


+

3
6 NH are ligands
Wh d l h ll d h When dissolve the yellow compound in water, the
total number of ions is 4 i.e. one complex ion and
h three counter ions.
If we add an excess amount of silver nitrate
(AgNO
3
) solution to this solution, we will obtain 3
moles of silver chloride (AgCl) as precipitate.
( ) ( )
2
2
H O
C NH Cl Cl C NH Cl 2Cl
+


+

( ) ( )
2
3 2 3 (aq)
5 5
(aq)
Co NH Cl Cl Co NH Cl 2Cl
d l li d

+

3
5 NHand 1 Cl are ligands

When dissolve the pink compound in water, the


total number of ions is 3 i.e. one complex ion and
two counter ions.
If we add an excess amount of silver nitrate
(AgNO
3
) solution to this solution, we will obtain 2
moles of silver chloride (AgCl) as precipitate.
Coordination number Coordination number
The number of bonds formed by metal ions to
ligandsin complex ions
The coordination number of the central metal varies
depending on the size charge and electron depending on the size, charge and electron
configuration of the transition metal ion.
M t l i h th di ti Many metal ions show more than one coordination
number, and there is no simple way to predict what
h di i b ill b i i l the coordination number will be in a particular case.
The typical coordination number are 2, 4 and 6.
See table 2.4
Complex ions Coordination number
( )
3
2
2
+


Ag NH
( )
2
3
4
4 Pt NH
+


( )
3
6 Co NH
+


( )
3
6
6 Co NH


( )
2
2 2 2 2
2
4 Pt H NCH CH NH
+


Type of ligand Type of ligand
Monodentate or unidentate ligand can form one
bond to a metal ion
Bidentate ligand can form two bonds to a metal ion
Polydentate ligand can form two bonds or more to Polydentate ligand can form two bonds or more to
a metal ion
Examples of monodentate ligands a p es o o ode a e ga ds
Examples of bidentate ligangs a p es o b de a e ga gs
Example of polydentate ligang a p e o po yde a e ga g
Chelate Chelate
A complex formed by polydentate ligands is frequently quite
stable and is called a chelate.
l d t t li d ft ll d h l ti t polydentate ligands are often called chelating agents
[Co(en)
3
]
3+
[Co(EDTA)]

Formulas and names of coordination


compounds
Every compound has a unique name and
a structural formula. a structural formula.
Use the name when talking and use the
formula when writing:
Write : [Cu(CN)
4
(H
2
O)
2
]Cl
2
Write : [Cu(CN)
4
(H
2
O)
2
]Cl
2
Call : Diaquatetracyanocopper (VI) chloride
Examples: a p es
Writing formula Writing formula
The cation is written before the anion
The charge of the cation(s) is balanced by the The charge of the cation(s) is balanced by the
charge of the anion(s)
In the complex ion metal is written before ligands In the complex ion, metal is written before ligands
and the whole ion is placed in brackets.
[ ]
2 3 2 4
K Co(NH ) Cl
[ ]
3 4 2
Co(NH ) Cl Cl
[ ][ ]
3 4 4
Pt(NH PdCl )
Naming Rules
1 Th i i d b f h i
Naming Rules
1. The cation is named before the anion.
[ ]
Cl Co(NH ) Cl
[ ]
3 4 2
Cl
chloride
Co(NH ) Cl
tetraamminedichlorocobalt(III) the name is

_
t theonlyspaceinthenameappearsbetweenthecationandtheanion notetha
ani
cati
n o
on
_
_
t the only space in the name appears between the cation and the anion note tha
[ ]
6 4
K Fe(CN)
[ ]
6 4
potassium
( )
hexacyanoferrate(II) the name is
_ _
ca anion tion
_ _
Naming Rules
2 Th f l i f i
Naming Rules
2. The name of complex consists of two parts written
together as one word. Ligands are named first
d h l i i d d and the metal ion is named second.
[ ]
3 4 2
Co(NH ) Cl
the name is tetraamminedichlorocobalt(III) ion
+
ligand name
metal name
( )
_
_
[ ]
4
6
Fe(CN)
thenameis hexacyanoferrate(II) ion

ligand namemetal name


the name is hexacyanoferrate(II) ion
__
Ligands name
3 Th l li d i f G k
Ligand s name
3. The complete ligand name consists of a Greek
prefix denoting the number of ligands, followed
b h ifi f li d by the specific name of ligand.
[ ]
4
6
Fe(CN)

Greek
prefix ligand
th li d i h
ligand name
the ligand name is hexacyano
_
g
Ligands name
A l d d h h d
g
Anionic ligands ends an -o where there was an -ide
or an -ato where there was an -ate. Look:
Bromide, Br

: Bromo
Carbonate, CO
3
2
: Carbonato
3
Cyanide, CN

: Cyano
Thiocyanate, SCN

: Thiocyanato
Oxide, O
2
: Oxo
The neutral ligands keep their original names, with a few
exceptions:
Ammonia, NH
3
: Ammine
Carbon monoxide, CO: Carbonyl
Water, H
2
O: Aqua
Ligands name g
The prefixes mono-, di-, tri-, tetra-, penta-, and hexa- are used to
denote the number of simple ligands
Greek
fi
ligand
[ ]

-
4
6
6
CN li d
prefix
ligand
Fe(CN) the ligand name is hexa cyano


When the name of ligand already has a number prefix, the number
-
6
CN ligand
g y p ,
of ligands is denoted with bis (2), tris (3), tetrakis (4) and so forth.
The name of the ligand is followed in parentheses.
[ ]
3 3
Co(en) Cl
thenameis tris(ethylenediamine)cobalt(III) chloride

3
ligand name
the name is tris(ethylenediamine)cobalt(III) chloride
_
Ligands name g
When there are two or more types of ligands, the ligands are
written in alphabetical order (disregarding Greek prefixes).
[ ]
C ( ) Cl
+
[ ]
3 4 2
Co(NH ) Cl
the name is tetraamminedichlorocobalt(III) ion
+
ligand name
metal name
( )
ligandammineis rittenbeforeligandchloro
_
_
ligand ammine is written before ligand chloro
Metals name M
4. The complete metal name consists of the name of
metal, followed by the oxidation number of metal as , y
a Roman numeral in parentheses.
[ ]
3 4 2
Co(NH ) Cl
+
[ ]

3 4 2
cation
( )
the name is tetraamminedichlorocobalt (III) ion

oxidation
number 3
( )
Metals name M
In order to identify whether the complex ion is cation
or anion, the name of metal is ended with ate for
[ ]
3 4 2
Co(NH ) Cl
+
the anion.
[ ]

3 4 2
cation
Co(NH ) Cl
the name is tetraamminedichlorocobalt (III) ion

2
oxidation
number 3
( )
( )
2
2
5
anion
Co(H O) CN


the name is aquapentacyanocobaltate(III) ion

Metals name M
Where there is a Latin name for the metal, it is
usually used to name the anion.
Copper (cuprum): Cuprate
Gold (aurum): Aurate
[ ]
4
6
Fe(CN)

Gold (aurum): Aurate
Iron (ferrum): Ferrate
anion
the name is hexacyanoferrate(I I) ion
_
Lead (plumbum): Plumbate
Silver (argentum): Argentate
[ ]
2
2 5
Fe(H O) (OH)
thenameispentaaq ah dro oiron(III) ion
+
Silver (argentum): Argentate
Tin (stannatum): Stannate

cation
the name is pentaaquahydroxoiron(III) ion
Metals name M
Oxidation number of metal ion is calculated from
the total charge of the complex minus the total
charge of the ligands in the complex as follows;
[ ]
4
6
Fe(CN) the name is hexacyanoferrate(II) ion

_
anion
total charge of the complex = 4
t t l h f th li d 6 ( 1) 6

total charge of the ligands = 6 ( 1) 6


oxidation number of metal ion = ( 4) ( 6) 2
=
= +
Exercise: Some Coordination Complexes e c se So e Coo d a o Co p e es
molecular
formula
Metal ion Ligand
donor
atom
coordination
number
[ ]
3 2
Ag(NH )
+
[ ]
2
4
Zn(CN)

[ ]
2
6
PtCl

[ ]
2
3 6
Ni(NH )
+
Exercise: Exercise:
1. What is the systematic name of [Co(NH
3
)
3
Cl
3
]?
2. What is the systematic name of [Co(en)
2
Cl
2
]NO
3
?
3. What is the formula of
tetraamminebromochloroplatinum(IV) chloride?
4. What is the formula of
hexaamminecobalt(III) tetrachloroferrate(III)? ( ) ( )
St t d I i i Structures and Isomerism in
coordination compounds coordination compounds
Geometry of complex Geometry of complex
Coordination number
2 4 4 6
Geometry of complex Geometry of complex
Isomerism Isomerism
Isomers are two or more
species which have the
Two isomers of [Co(NH
3
)
4
Cl
2
]
+
same formula but exhibit
different properties
[ (
3
)
4 2
]
The different properties
are the result of different are the result of different
arrangements of atoms.
Are They Isomers? Are They Isomers?
In order to be isomers, the two compounds
must:
contain the same number and types of atoms, and
be non superimposable be non-superimposable.
Isomerism Isomerism
Structural isomerism: the isomers contain at least one
different connection or bonding.
Stereoisomerism: all of the connections (or bonding) Stereoisomerism: all of the connections (or bonding)
in the isomers are the same but the spatial
arrangements of the atoms are different (i e arrangements of the atoms are different (i.e.
different 3D-structure)
Structural isomerism Structural isomerism
Coordination isomerism:
The compositions of the complex ion are different
( ) ( )
( ) ( ) ( ) ( )
3 4 3 4
5 5
and Co NH SO Co NH S Br O Br



( ) ( ) ( ) ( )
3 3 3 3
Co en Cr ox and Cr en Co ox
en ethylenediamine


= en ethylenediamine
ox oxalate n io =
=
Structural isomerism Structural isomerism
Linkage isomerism:
The composition of the complex ion is the same but the point p p p
of attachment of at least one of the ligands differ
Ligands that can attach to metal ions in different ways are
thiocyanate (SCN

), cyanide (CN

), and nitrite ion (NO


2

).
( ) ( )
3 2
4


Co NH NO Cl Cl
( ) ( )
3
tetraamminechloro cobalt(III) chloride (yellow) nitrito-


N
Co NH ONO Cl Cl
( ) ( )
3
4
tetraamminechloro cobalt(III) chloride (red) nitrito-


Co NH ONO Cl Cl
O
Ligands That Can Form Linkage Isomers
ligand Lewis structure name donor atoms ligand Lewis structure name donor atoms
CN

cyanide ion C or N
SCN

thiocyanate
ion
S or N
NO
2

nitrite ion N or O
2
Stereoisomerism Stereoisomerism
G i l i i i i i Geometrical isomerism or cis-trans isomerism:
Atoms or groups have different positions around the
metal atom
Stereoisomerism Stereoisomerism
Stereoisomerism Stereoisomerism
Optical isomerism :
Optical isomers are isomers that are non-superimposable
mirror images of one another.
Optical isomers
[Co(en)
3
]
3+
p
Stereoisomerism Stereoisomerism
Optical isomerism :
Isomers which rotate plane-polarized light in
opposite directions with the same angle.
Chiral and Achiral Chiral and Achiral
the object and its mirror image are identical, it is
called achiral.
object whose mirror image is not identical with itself
is said to be chiral
Chiral and Achiral Chiral and Achiral
trans-isomer is achiral : diastereomers
cis-isomers are chiral : enantiomers
Racemic mixture
A compound whose solution rotates the plane of polarized light
Racemic mixture
A compound whose solution rotates the plane of polarized light
to the right (when looking toward the source of light) is called
dextrorotatory and is labelled d
A compound whose solution rotates the plane of polarized light
to the left is called levorotatory and is labelled l
A chemical reaction normally produces a mixture of equal y p q
amounts of optical isomers , called a racemic mixture.
A racemic mixture has no net effect on polarized light
Bonding in Coordination compounds
Valence Bond Theory
Th l b d t f h b idi ti th
Valence Bond Theory
The valence-bond concept of hybridization proposes the
mixing of particular combinations of s, p and d orbitals to
give hybrid-orbital sets of specific geometries give hybrid orbital sets of specific geometries.
For simple
compounds compounds
Valence Bond Theory
th f ti f di ti l t b d i
Valence Bond Theory
the formation of coordination covalent bond in a
complex,
a ligand orbital containing two electrons overlaps an
unoccupied (empty) orbital on the metal ion.
Orbital Hybridization Orbital Hybridization
Geometry of Coordination Hybridization
complex number
Linear 2 sp Linear
Tetrahedral
2
4
sp
sp
3
Square planar
Octahedral
4
6
dsp
2
d
2
sp
3
or sp
3
d
2
Octahedral 6 d sp or sp d
Linear Complexes: sp hybridization
F di ti b 2
Linear Complexes: sp hybridization
For coordination number 2
2 ligands need 2 hybrid orbitals to share electrons with the
metal atom metal atom
Tetrahedral Complexes: sp
3
hybridization
F di ti b 4
Tetrahedral Complexes: sp hybridization
For coordination number 4
4 ligands need 4 hybrid orbitals to share electrons with the
metal atom metal atom
For d
10
ion, the complex form tetrahedral geometry
Squareplanar Complexes: dsp
2
hybridization
F di ti b 4
Squareplanar Complexes: dsp hybridization
For coordination number 4
4 ligands need 4 hybrid orbitals to share electrons with the
metal atom metal atom
For d
8
ion, the complex form square planar geometry
Octahedral Complexes: d
2
sp
3
hybridization Octahedral Complexes: d sp hybridization
For coordination number 6
6 ligands need 6 hybrid orbitals to share electrons with the
l metal atom
Consider octahedral complex of Fe
2+
ion
3
4
4 4
d
p
s d

2

ion Fe
+

4
4d
3
4 4
p
d
s d

3 2

d

_
3 2
sp d
4
3
p
d

4
3
3
4 4

p
d
d
s d


2 3
d sp
_
4p
4d
3d 4s
4d

3 2
d

_
( )
2
3 2
spd
Fe HO 4unpairedelectrons
+


( )
2
6
Fe HO 4 unpaired electrons


4p
3d
3d 4s
4d


2 3
d

_
( )
4
2 3
dsp
Fe CN nounpairedelectrons



( )
6
Fe CN no unpaired electrons


Crystal Field Theory
Th l b d th t f ll l i th ti f
Crystal Field Theory
The valence bond theory cannot fully explain the properties of
complex ions such as colour and magnetism.
The crystal field model focuses on the energies of the d The crystal field model focuses on the energies of the d
orbitals.
This model assumes that the ligands can be approximated by
negative point charges and that metal-ligand bonding is
entirely ionic.
Th t t f l t t ti i t ti There are two types of electrostatic interaction
One is the attraction between the positive metal ion and the
negatively charge ligands. g y g g
Two is the electrostatic repulsion between the lone pairs on the
ligands and the electrons in the d-orbitals of the metals.
d-orbitals splitting d orbitals splitting
Octahedral complexes
The two of the orbitals, d
z
2
and d
x
2
-y
2
, point their lobes
y
directly at the point-charge ligands.
The other three orbitals, d
xy
, d
yz
, and d
xz
, point their lobes
between the point charges.
d-orbitals splitting d orbitals splitting
The negative point charge ligands repel negatively
charged electrons.
The negative point charge ligands increase the
energies of all the d orbitals. g
the orbitals that point at the ligands are raised in
energy more than those that point between the ligands. e e gy o e a ose a po be wee e ga ds.
It i thi litti f th 3d bit l i It is this splitting of the 3d orbital energies
(symbolized by ) that explains the colour and
magnetism of complex ions of the first transition metal magnetism of complex ions of the first transition metal
ions.
d-orbitals splitting d orbitals splitting
The splitting of d orbitals determine the
arrangement of electrons in these orbitals.
Electrons occupy orbitals singly as long as empty
orbitals of equal energy are available. orbitals of equal energy are available.
The repulsive pairing energy (E
pairing
) must be
overcome for two electrons to occupy the same overcome for two electrons to occupy the same
orbital.
d
1
d
3
ions d d ions
d
1
d
2
d
3
d d d
d
d 2 2 2
d
d 2 2 2
d
d 2 2 2
d
z
d
x - y
2 2 2
d
z
d
x - y
2 2 2
d
z
d
x - y
2 2 2
d
xy
d
xz
d
yz
d
xy
d
xz
d
yz
d
xy
d
xz
d
yz
d
4
d
z
d
x - y
2 2 2
d
z
d
x - y
2 2 2
small
large
d d d d
xy
d
xz
d
yz
d
xy
d
xz
d
yz
high spin complex low spin complex
Example 2.1
Th [F (CN) ]
3
i i k h i d
Example 2.1
The [Fe(CN)
6
]
3-
ion is known to have one unpaired
electron. Does the CN
-
ligand produce a low-spin or
h h ? high-spin case?
Exercise Exercise
How many lone-paired electron in high-spin and
low-spin arrangement of Co
2+
?
Describe the distribution of d-electrons in Describe the distribution of d-electrons in
[Ni(H
2
O)
6
]
2+
, using crystal field theory.
Spectrochemical series: Spectrochemical series:
From studies of many octahedral complexes, The
ligands are arranged in order of decreasing
values toward a given metal as follows:
- - - - - - -
2 3 2
CO> CN > NO >en > NH > H O> OH > F > Cl > Br >I
strong fi el d
l arge
wea

k fi el d
s mall
Example:
h bl l h l h l 3d
3 6
Co d ion
+

There are two possible ways to place the electrons in the split 3d
orbitals
Example 2.2 Example 2.2
Predict the number of unpaired electrons in the
[Cr(CN)
6
]
4-
d-orbital splitting: Tetrahedral complexes
Th d bit l litti i it t th t f
d-orbital splitting: Tetrahedral complexes
The d-orbital splitting is opposite to that for
octahedral arrangement
None of 3d orbitals point
their lobes directly at the y
point-charge ligands. Thus the
splitting of d-orbitals in
tetrahedral arrangement is
smaller than in octahedral
arrangement
Only high spin complexes
arrangement.
are observed
2
z
d
2 2
x y
d

EE
xz
d
yz
d
xy
d
oct
tet
d d d d d
xz yz xy
tet
xz
d
yz
d
xy
d
2
z
d
2 2
x y
d

Octahedral case Tetrahedral case


Example 2.3 Example 2.3
Give the crystal field diagram for the tetrahedral
complex ion of CoCl
4
2-
Square Planar complex Linear complex
Only low spin complex have
been found
Example 2.4 Example 2.4
Use crystal field theory to describe the d-electron
distributions of the complexes
( ) ( )
2 2
3
4 4
Ni NH and Ni CN
+


The tetraamminenickel(II) ion is paramagnetic, and
th t t i k l t (II) i i di ti the tetracyanonickelate(II) ion is diamagnetic.
Colour in complexes Colour in complexes
Objects appear coloured in white light because they
absorb certain wavelengths and reflect or transmit
others: an opaque object reflects light, whereas a
clear one transmits it.
The reflected or transmitted light enters the eyes g y
and is perceived as colour by the brain.
The complex ion shows colour because it absorbs certain wavelengths of light
in the visible region, the colour of that substance is determined by the
wavelengths of visible light that remain.
Relation between absorbed and observed colours
The reason that the ion absorbs specific wavelengths of visible light
causes by the transfer of the lone d electron between the split d orbitals causes by the transfer of the lone d electron between the split d orbitals
( )
3
3 1
2
6
Ti H O is violet, Ti d ion
+
+



2
z
d
2 2
x y
d

E

2
z
d
2 2
x y
d

h
d d d
E
d d d
xz
d
yz
d
xy
d
xz
d
yz
d
xy
d
( )
3
Ground state
+

( )
3
Excited state
Ti H O
+

( )
2
6
Ti H O



( )
2
6
Ti H O



Visible spectrum of [Ti(H
2
O)
6
]
3+
p [ (
2
)
6
]
The (or E energy spacing in the molecule) relates to the ( gy p g )
wavelength of light by
1
wavelengthof light
If the changes, the of light to be absorbed changes
, wavelength of light =

If the changes, the of light to be absorbed changes


therefore the colour changes.
Since the ligands coordinated to a given metal ion determine g g
the size of d-orbital splitting (), the colour changes as the
ligands are changed.
( )
2 3
6
Cr H O Cl Violet


Observed colour
( )
( )
6
2 2
5
Cr H O Cl Cl Blue-green



( )
2 2
4
Cr H O Cl Cl Green


- - - - - - -
2 3 2
st r ong fi el d
CO > C N > NO > en > NH > H O >
we
OH > F >
ak f
Cl > Br > I
i el d st r ong fi el d
l ar ge
we

ak f

i el d
s ma ll
Li ht b b d b l ith diff t li d Light absorbed by complexes with different ligands
Colour of Complexes with different ligands
Is this correct? Is this correct?
Compound
3
2 6
[Ti(H O) ]
+ 3
6
[Ti(CN) ]

Wavelength
absorbed
500 nm 450 nm