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Transition Metals &

Coordination Compounds
CHM361: Inorganic Chemistry

Topic Outline

Transition Metals
Coordination Compounds
Isomerism
Bonding in Complex Ions

Transition Metals

Transition Metals
Transition
metals
typically have
incompletely
filled d
subshells or
readily give
rise to ions
with
incompletely
filled d
subshells

Transition Metals Electron


Configuration

Transition Metals Electron


Configuration
The d-block elements have the general
electron configuration of: [Noble gas] ns2 (n1)dx,
where x = 1-10, n = 4-7

Transition metals form ions


through the loss of the ns
electrons before the (n 1)d
electrons.

Transition Metals Electron


Configuration
Write the subshell electron configurations
for:
Cu
Cr3+
Mn4+

Transition Metals Oxidation


States

Transition Metals Oxidation


States
Most transition metals have multiple oxidation
states
The highest oxidation state for elements in Groups
3B(3) through 7B(7) equals the group number
These states are seen when the elements combine
with the highly electronegative oxygen or fluorine
Elements in Groups 8B(8), 8B(9) and 8B(10) exhibit
fewer oxidation states. The higher oxidation state is
less common and never equal to the group number

Transition Metals Oxidation


States

+2
Mn2+

+6

MnO4

+7
MnO4

The highest oxidation state


for Mn equals its group
number.

Transition Metals Properties


All transition metals are metals,
whereas main-group elements in each
period change from metal to nonmetal
Many transition metal compounds are
coloured and paramagnetic, whereas
most main-group ionic compounds are
colourless and diamagnetic

Transition Metals Periodic


Trends
Across a period the following trends are
observed:
Atomic size decreases at first, then remains
relatively constant.
The d electrons fill inner orbitals, so they shield outer electrons very
efficiently and the 4s electrons are not pulled closer by the increasing
nuclear charge

Electronegativity and ionisation energies also


increase relatively little across the transition
metals of a particular period

Transition Metals Periodic


Trends

Transition Metals Periodic


Trends
Within a group the trends also differ from
those observed for main group elements
Atomic size increases from Period 4 to 5, but not
from Period 5 to 6.
A Period 6 element has 32 more protons than its
preceding Period 5 group member instead of only 18.
The extra shrinkage from the increase in nuclear
charge (called the lanthanide contraction) is
roughly equal to the normal size increase due to
adding an extra energy level.

Transition Metals Periodic


Trends
Electronegativity increases within a group from
Period 4 to 5, then generally remains unchanged
from Period 5 to 6. The heavier elements often
have high EN values.
Ionisation energy values generally increase down a
transition group, also running counter to the main
group trend
Density increases dramatically down a group since
atomic volumes change little while atomic masses
increase significantly

Transition Metals Periodic


Trends

Transition Metals Metallic


Behaviour
The lower the oxidation state of the transition
metal, the more metallic its behaviour
Ionic bonding is more prevalent for the lower
oxidation states, whereas covalent bonding
occurs more frequently for higher oxidation
states
Metal oxides become less basic (more acidic)
as the oxidation state increases

Coordination Compounds
A coordination compound (or
complexes) typically consists of a complex
ion and a counter ion
A complex ion contains a central metal
cation bonded to one or more molecules or
ions, called ligands
A ligand has at least one unshared pair of
valence electrons

Coordination Compounds

H
Examples of ligands

Example of a complex ion

Cl

Coordination Compounds
The complex ion is
associated with counter
ions of opposite charge
The complex ion
[Cr(NH3)6]3+ has a central
Cr3+ ion bonded to six NH3
ligands. The complex ion
behaves like a polyatomic
ion in solution

Coordination Compounds

[Co(NH3)6]Cl3 dissolves in water. The


six ligands remain bound to the

Coordination Compounds
The atom in a ligand that is bound directly to
the metal atom is the donor atom

Ligands with one donor atom is called


monodentate, two donor atom is called
bidentate, and three donor atom or more is
called polydentate/multidentate

Coordination Compounds

Coordination Compounds
Bidentate and
polydentate ligands are
called chelating agents
[Co(en)3]2+

[PbEDTA]2-

Coordination Compounds
Coordination Number
The coordination number is the number of
ligand atoms bonded directly to the
central metal ion
Coordination number is specific for a given
metal ion in a particular oxidation state and
compound
The most common coordination number in
complex ions is 6, but 2 and 4 are often seen

Coordination Compounds
Oxidation Number
The net charge of a complex ion is the sum
of charges on the central metal & its ligands
In [Pt(Cl)6]2-, the oxidation number of Cl is -1,
therefore for Pt = -2 + 6(1) = +4
If the ligands have no charge, then the
oxidation number for the metal is the same
as the charge of the complex ion, such as in
[Cu(NH3)4]2+, where the oxidation number of
Cu is +2

Coordination Compounds Nomenclature


Rules for naming complexes:
The cation is named before the anion
Within the complex ion, the ligands are named first, followed
by the metal ion.
The ligands are named in alphabetical order. Neutral ligands
usually retain its own name (with some exceptions). Anionic
ligands drop ide to change with o
Add numerical prefixes if there is more than 1 for each ligand.
Di-, tri-, tetra-, etc
Bis-, tris-, tetrakis-, etc if the ligand already contain numberical
prefix, such as ethylenediamine. The name of the ligand is written
in parentheses

Coordination Compounds Nomenclature


Rules for naming complexes:
The oxidation state of the metal is written in
Roman numeral (in parentheses) if the metal
has more than 1 oxidation state
If the complex ion is an anion, the name of the
metal will end with -ate

Coordination Compounds Nomenclature

Name

Formula

Aqua

H2O

Ammine

NH3

Carbonyl

CO

Nitrosyl

NO

Special Names for Neutral Molecules

Coordination Compounds Nomenclature


Name

Formula

Fluoro

F-

Chloro

Cl-

Bromo

Br-

Iodo

I-

Nitro

NO2-

Nitrato

NO3-

Carbonato

CO32-

Acetato

CH3COO-

Hydroxo

OH-

Cyano

CNCommon Anionic Ligands

Coordination Compounds Nomenclature


Name

Formula

Aluminium

Aluminate

Chromium

Chromate

Cobalt

Cobaltate

Copper

Cuprate

Gold

Aurate

Iron

Ferrate

Lead

Plumbate

Nickel

Nickelate

Silver

Argentate

Tin

Stannate

Zinc

Zincate
Metals in Complex Anions

Coordination Compounds Nomenclature


Example:
Write the systematic name for [Cr(H2O)4Cl2]Cl .
Step 1: Find the oxidation number for Cr = +1 + 2(1) =
+3
Step 2: Find out whether complex ion is anion or cation.
Its a cation, therefore the complex is named first
Step 3: Name the ligand in alphabetical order
tetraaquadichlorochromium(III)
Step 4: Name the whole complexes
tetraaquadichlorochromium(III) chloride

Coordination Compounds Nomenclature


Example:
Write the systematic name for (NH4)2[Pt(OH)6].
Step 1: ON for Pt = -2 + 6(1) = +4
Step 2: The complex is an anion, thus it is put after the
cation.
Step 3: Remember, the ligand is anion. So the name is
hexahydroxoplatinate(IV)
Step 4: The name of the complex is ammonium
hexahydroxoplatinate(IV)

Exercises
Name the following compounds:
[Cr(NH3)3]Cl3
[Pt(en)]Cl2
K2[Cu(C2O4)Br2]
NH4[Fe(OH)4]

Coordination Compounds Formula


When writing the formula for a coordination
compound
the cation is written before the anion,
the charge of the cation(s) is/are balanced by
the charge of the anion(s), and
The central atom is written first, followed by
neutral ligands, then anionic ligands, and the
formula of the whole complex ion is placed in
square brackets.

Coordination Compounds Formula


Example: Write the formula for
tetraamminebromochloroplatinum(IV) chloride.
Step 1: Write the complex ion formula, starting with
metal, then neutral, then anion Pt(NH 3)4BrCl
Step 2: Determine the charge of the complex ion = +4
+ 4(0) + (-1) + (-1) = +2
Step 3: Balance the charges with counter ion. Since
the cation is +2, then the anion should be 2 (-1).
Step 4: Write the whole formula [Pt(NH 3)4BrCl](Cl)2

Exercises
Write the formula for the following
compounds:
Hexacarbonylmanganese(I) perchlorate
Tris(ethylenediamine)copper(II) sulfate
Potassium diaquatetracyanocobaltate(III)

Coordination Compounds Geometry


The geometry depends on coordination
number and type of ion

Coordination No = 2

Coordination No = 4

Coordination No = 6

Isomerism
Isomers are compounds with the same
chemical formula but different in chemical
properties
The two main types of isomers in
coordination compounds are:
Structural/constitutional isomers: where atoms
are connected differently
Stereoisomers: where the arrangement in
space is different

Isomerism Structural Isomers

Structural isomers occur when the atoms are


connected in a different way
For coordination compounds, there are 4
types of structural isomers:

Coordination isomers
Ionisation isomers
Hydrate isomers
Linkage isomers

Isomerism Structural Isomers

Coordination isomers when the


composition of the complex ion, but not of
the compound, is different
It can occur by exchange of ligands between
complex ions, ie. [Cr(NH3)6][Co(CN)6] &
[Co(NH3)6][Cr(CN)6]

Isomerism Structural Isomers

Ionisation isomers similar with coordination


isomers, when the composition of the
complex ion, but not of the compound, is
different
It can occur by exchange of ligand and
counter ion, ie. [Pt(NH3)4Cl2](NO2)2 &
[Pt(NH3)4(NO2)2]Cl2

Isomerism Structural Isomers


Hydrate isomers similar with coordination isomers,
when the composition of the complex ion, but not of the
compound, is different
It can occur by exchange of water in complexes with
water in hydrates
A good example is CrCl3.6H2O, where the coordination
compound can contain 4,5 or 6 water molecules
[CrCl2(H2O)4]Cl.2H2O
bright-green
[CrCl(H2O)5]Cl2.H2O grey-green
[Cr(H2O)6]Cl3 violet
These isomers have different physical & chemical
properties

Isomerism Structural
Isomers
Linkage isomers the composition of
complex ion is the same, but the ligand
donor atom is different, ie.

Isomerism - Stereoisomers
Geometric isomers (also called cis-trans
isomers or diastereomers) atoms/group of
atoms arrange differently in space relative to
the central ion

The cis and trans isomers of [Pt(NH3)2Cl2].

Isomerism - Stereoisomers
Optical isomers (also called enantiomers)
when a molecule and its mirror image cannot
be superimposed
Optical isomers are physically identical,
except for the direction they rotate polarised
light
A way to determine optical isomerism is by
rotating one molecule on its vertical axis to
see whether it can be superimposed on the
other

Isomerism - Stereoisomers

Isomerism - Stereoisomers

Isomerism - Stereoisomers

Draw stereoisomers for


each of the following and state
the type of isomerism:

Example:

[Pt(NH3)2Br2] (square planar)


[Cr(en)3]3+ (en = H2NCH2CH2NH2)

Isomerism - Stereoisomers
The square planar Pt(II) complex has two different
types of monodentate ligands. Each pair of
ligands can be next to each other or across from
each other. Thus geometric isomerism occurs.
They do not have optical isomers since each
compound is superimposable on its mirror image.

Isomerism - Stereoisomers
Ethylenediamine (en) is a
bidentate ligand. The Cr3+
ion has a coordination
number of 6 and an
octahedral geometry. The
three bidentate ligands
are identical, so there is
no geometric isomerism.
However, the complex
ion has a
nonsuperimposable
mirror image. Thus
optical isomerism
occurs.

Bonding in Complex Ions: VB


Theory
In the formation of complex ion, the filled
ligand orbital overlaps with empty metal
orbital
The ligand becomes a Lewis base, which
donates an electron pair
The metal becomes a Lewis acid, which
accepts the electron
Thus, the bond between them is called
coordinate covalent bond

Bonding in Complex Ions: VB


Theory
Complex geometry can be linked to 5 types
of hybrids:
Coordinati Hybrid
on
Orbitals
Number

Geometry

Example

sp

Linear

[Ag(NH3)2]+

sp3

Tetrahedral

[COCl4]2-

dsp2

Square
planar

[Ni(CN)4]2-

d2sp3 or
sp3d2

Octahedral

[Cr(H2O)6]3+
,
[Co(H2O)6]2

Bonding in Complex Ions: VB


Theory (Tetrahedral Complexes)
Metal ions with filled d orbital often form
tetrahedral complexes, such as Zn2+

Bonding in Complex Ions: VB


Theory (Square Planar Complexes)

Metal ions with a d8 configuration usually


forms square planar complexes

Bonding in Complex Ions: VB


Theory (Octahedral Complexes)
The octahedral can occur in two ways :
d2sp3, where the principal quantum number of
d orbital is lower than s and p orbitals, and
form low spin complex
sp3d2, where the principal quantum number of
d orbital is the same with s and p orbitals, and
form high energy spin

Bonding in Complex Ions: VB


Theory (Octahedral Complexes)
An example of d2sp3 complex is [Cr(NH3)6]3+
ion.

Bonding in Complex Ions: VB


Theory (Octahedral Complexes)
An example of sp3d2 complex is [CoF6]3- ion.

Bonding in Complex Ions: VB


Theory (Octahedral Complexes)
An example of d2 sp3 complex is [Co(CN)6]3ion.

Bonding in Complex Ions: VB


Theory (Octahedral Complexes)
For octahedral complexes, you can only
decide on the hybrid orbitals if you know
whether the ion is diamagnetic or
paramagnetic
To determine this property, you will have to
know whether the ligand is a strong field
ligand or a weak field ligand strong field
ligand tends to form diamagnetic ion

Bonding in Complex Ions: Crystal


Field Theory
Crystal field theory provides insights on the
different colours produced by transition
compounds and their magnetic properties
This theory highlights the effects on d orbital
energies of the metal as the ligands
approach

Bonding in Complex Ions: Crystal


Field Theory
Crystal field model: the properties of the
complexes result from the splitting of d
orbital energies, which arises from
electrostatic attractions between the metal
cation and the negative charge of the
ligands
The ligands can be anionic ligand, with full
negative charge like F-, or partially charged,
like NH3

Bonding in Complex Ions: Crystal


Field Theory
In isolated ion, the d orbitals are said to have
similar energies. But try to picture 6 ligands
approaching a metal cation from 6 different
directions to form an octahedral complex.
Because of different orientation of d orbitals,
the ligands are repelled unequally.

Bonding in Complex Ions: Crystal


Field Theory

Bonding in Complex Ions: Crystal


Field Theory
As a result of the different orientations,
electrons in B & C experience stronger
repulsion than D,E & F.

Bonding in Complex Ions: Crystal


Field Theory
The two higher energy orbitals are eg
orbitals, arising from B & C orientations
The three lower energy orbitals are t2g
orbitals, arising from D, E & F orientations
The splitting of orbital energies is called
crystal field effect
The energy difference between eg and t2g
orbitals is the crystal field splitting energy
()

Bonding in Complex Ions: Crystal


Field Theory

Different ligands
create crystal field of
differing strengths:
Strong field ligands:
larger splitting energy
Weak field ligands:
smaller splitting
energy

Bonding in Complex Ions:


Coloured Compounds

White light consists


of all wavelengths
in the visible range
It can be dispersed
into different
colours with
different
wavelengths

Bonding in Complex Ions:


Coloured Compounds
What you see is actually the colour that is
reflected/transmitted
From the colour wheel, you can see that each
colour has its complementary (opposite) colour
The colour that you see is the result of:
The object transmitting that particular colour it
absorbs all other colours
The object absorbing light of a particular colour
it reflects the complementary colour

Bonding in Complex Ions:


Coloured Compounds

Bonding in Complex Ions:


Coloured Compounds
The colour of coordination compound is
determined by of its complex ion
When an ion absorbs energy, it can move
from lower energy t2g level to higher energy
eg level

Bonding in Complex Ions:


Coloured Compounds
Take [Ti(H2O)6]3+ ion as an example
It appears purple in aqueous solution
Hydrated Ti3+ has its one d electron in t2g
orbital, and the value corresponds to
green-yellow range
When light is absorbed in this range, red,
blue and violet light is transmitted the
solution appears to be purple

Bonding in Complex Ions:


Coloured Compounds

Bonding in Complex Ions:


Coloured Compounds
Two key observations for coloured
compounds:
For a given ligand, colour depends on the
oxidation state of the metal ion
For a given metal ion, colour depends on the
ligand

Bonding in Complex Ions:


Coloured Compounds

[V(H2O)6]

[V(H2O)6]

2+

3+

A change in oxidation
state causes a change in
color.

[Cr(NH3)6]

[Cr(NH3)5Cl ]

3+

2+

Substitution of an NH3
ligand with a Cl- ligand
affects the color of the
complex ion.

Bonding in Complex Ions:


Coloured Compounds
A spectrochemical series is created due to the fact that colour
depends on the ligand
This series rank the ability of a ligand to split d orbital energies

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

LONGER

STRONGER
FIELD
LARGER
SHORTER

Bonding in Complex Ions:


Magnetism
Magnetic properties are determined by the number of
unpaired electrons in the d orbitals of the metal ion
Hunds rule states that e- occupy orbitals of equal
energy one at a time. When all lower energy orbitals are
half-filled:
The next e- can enter a half-filled orbital and pair up by
overcoming a repulsive pairing energy, (Epairing).
The next e- can enter an empty, higher, energy orbital by
overcoming .

The number of unpaired e- will depend on the relative


sizes of Epairing and .

Bonding in Complex Ions:


Magnetism
Weak field ligands have small , so it is
easier to jump to eg orbital and stay unpaired
create high spin complexes, with
maximum number of unpaired electrons
Strong field ligands have big , so it takes
more energy to jump to eg than stay paired
in t2g create low spin complexes, with
fewer unpaired electrons

Bonding in Complex Ions:


Magnetism

Bonding in Complex Ions:


Magnetism
The low-spin and high-spin complexes are
possible for only d4,d5,d6 and d7 ions
The rest all form high spin complexes since
the number or unpaired electrons will be
similar with its free ion

Bonding in Complex Ions:


Magnetism
high spin:
weak-field
ligand

low spin:
strongfield
ligand

high spin:
weak-field
ligand

low spin:
strongfield
ligand

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