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Module 3

Module 3 of symmetry operation

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0% found this document useful (0 votes)
26 views16 pages

Module 3

Module 3 of symmetry operation

Uploaded by

Abefe Adesoji
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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MODULE THREE

INTRODUCTION TO COORDINATION COMPOUNDS II

 Unit One – What are coordination compounds?


 Unit Two – Naming coordination compounds
 Unit Three – (A) Coordination number and molecular structure
(B) Types of ligands
 Unit Four –Isomerism in coordination compounds
 Unit Five – Crystal field theory

UNIT ONE: What are Coordination Compounds?


Double salts and coordination complexes can appear similar especially in writing their
formulae e.g. KCl.MgCl.6H2O and Fe(CN)2.4KCN. However, KCl.MgCl.6H2O is a
double salt when it’s dissolved in water it gives rise to K+, Mg+, Cl- ions. Whereas
Fe(CN)2.4KCN when dissolved in water does not form K+, Fe2+, and CN- ions but
rather K+ and [Fe(CN)6]4-. [Fe(CN)6]4- is a complex ion, hence Fe(CN)2.4KCN is a
coordination compound and is better written as K4[Fe(CN)6].
Coordination complexes are compounds which consist of a central metal atom or ions
surrounded by a definite number of electron donating molecules or ions. These
molecules or ions surrounding the metals are referred to as ligands. The central metal
is usually transition metals this is because of the presence of vacant d or f orbitals for
the ligands to donate their electrons. A coordination complex maybe a neutral molecule
or an ion and if it is positively charged it is called a cationic complex while the negatively
charged complex is called an anionic complex.
The interaction between the metal atom and ligand are considered to be as Lewis acid-
base reaction. Lewis bases are electron pair donor while Lewis acids are electron pair
acceptor. So the ligands are Lewis base and the central metals are Lewis acid.
The charge on the complex must be equal to the sum of the charge on the central ions
and the charges (if any) on the ligand e.g. [Fe(CN)6]4- charge on Fe is +2 and charge on
CN is -1
+2 + (6 × −1) = −4
The number of ligands surrounding the central metal is called the coordination
number of the complex and this is different from oxidation number of the complex.
[Fe(CN)6]4-
-4 is the oxidation number of the complex ion
6 is the coordination number.
Oxidation number is referred to as the Primary/Principle Valence while coordination
number is referred to as Secondary/Auxiliary valence. Primary valences are non-
directional while secondary valences are directional.

Werner’s Theory of Coordination Compounds


Alfred Werner got the Nobel prize of chemistry in 1913 for his coordination theory of
transition metal-amine complexes. He carried out a series of experiments with reacting
CoCl3 and various concentrations of ammonia form various amminechlorocobalt(III)
complexes then titrating against AgNO3 to determine the amount of chloride in the
solution. For 3 different solutions he found that each had varied concentration of
chloride ion. One had an equivalent of 3 moles of chloride ion, the other 2 moles and
another just 1 mole. He concluded that the structure of these complexes were as
2+ +
3+ NH3
NH3
NH3
NH3 Cl
H3N H3N
NH3
H3N + Co
2+ Co
Co
Cl2 Cl Cl
H3N Cl H3N
H3N NH3 Cl3
NH3 NH3
NH3
2 2
2 -
In solution 3 moles of Cl- is produced In solution 2 moles of Cl- is produced In solution 1 mole of Cl is produced

Postulate of Werner’s theory


1. In coordination compounds, the central metal atoms exhibit primary valence and
secondary valence. The primary valence is ionizable and the secondary one is
not. The primary valence corresponds to oxidation state the secondary valence
corresponds to the coordination number.
2. Every metal atom has a fixed number of secondary valences (coordination
number(s)).
3. The metal atom tends to satisfy both its primary valence as well as the secondary
valence. The primary valence is satisfied by negative ions because the metal ion
has positive charge whereas the secondary valence is satisfied either by negative
ions or by neutral molecules.
4. The secondary valences are always directed towards the fixed position in the
space and this lead to definite geometry of the coordination compound.
Limitation of Werner’s theory
1. It failed to explain why all elements do not form coordination compounds.
2. It failed to explain the directional properties of bond in coordination
compounds.
3. It does not explain the colour, magnetic and optical properties of these
compounds.
UNIT TWO - Naming Coordination Compounds

The rules for naming coordination compounds are as following:

1. The cation is named before the anion. This rule holds whether the complex ion
is negatively charged or positively charge. For example, in K 4[Fe(CN)6] and
[Co(NH3)4Cl2]Cl; K+ and [Co(NH3)4Cl2]+ are the cations and are named first.

2. Within a complex ion the ligands are named first, in alphabetical order, and the
metal ion is named last.
Ligand Abbreviation Name of ligand in
coordination compound
Bromide Br -
Bromo
Chloride Cl -
Chloro
Cyanide CN -
Cyano
Hydroxide OH -
Hydroxo
Oxide O 2-
Oxo
Carbonate CO2 3-
Carbonate
Nitrite NO 2-
Nitro
Oxalate C2O4 2-
[ox] 2-
Oxalato
Ammonia NH3 Ammine
Carbon monoxide CO Carbonyl
Water H2O Aquo
Ethylenediamine H2NCH2CH2NH2 en Ethylenediamine
Acetylacetonate CH3COCH2COCH3 [acac] -
Acetoacetate
Ethylenediaminetetraacetate [EDTA] 4-
Ethylenediaminetetraacetate
( OOC)2NCH2CH2N(COO )2
- -

3. The names of the anionic ligand end with the letter o, whereas a neutral ligand is
usually called by the name of the molecule except for H2O, CO, and NH3.

4. When there are more than one ligands present, we use the Greek prefixes di-(2),
tri-(3), tetra-(4), penta-(5), and hexa- (6) to name. For example [Co(H2O)6]3+ will
be hexaaquocobalt.

5. When there are different ligands the ligands are names in alphabetical order. Thus
the ligands in the cation [Co(NH3)4Cl2]+ are “tetraamminedichloro”.
6. If the name of the ligand contains a Greek prefix, we use the prefixes bis-(2), tris-
(3), and tetrakis-(4) to indicate the number of ligands present. For example, the
ligand ethylenediammine already contain the word ‘di’ which is a Greek word
therefore if two of such ligands are present, the name will be bis(ethylenediammine).

7. The oxidation number of the metal in Roman numerals following the name of
the metal. For example the Roman numerals III is used to indicate the +3
oxidation state of Co in [Co(NH3)4Cl2]+ which is called tetraaminedichlorocobalt(III)
ion.

8. If the complex is an anion, its name ends in –ate. For example, in K4[Fe(CN)6],
the anion [Fe(CN)6]4- is called hexacyanoferrate(II) ion. Note that the Roman
numeral II indicates the oxidation state of iron.

Metal Names of metal in anionic complex


Aluminum Aluminate
Chromium Chromate
Cobalt Cobaltate
Copper Cuprate
Gold Aurate
Iron Ferrate
Lead Plumbate
Manganese Manganate
Molybdenum Molybdate
Nickel Nickelate
Silver Argentate
Tin Stannate
Tungsten Tungstate
Zinc Zincate
UNIT THREE – (A) Coordination Number and Molecular Structure
With the coordination number it is possible to predict the shape/structure of a
complex. However further experimental data will be required to confirm the structure.
Note here we will discuss only coordination number 2 - 6, however there are high
coordination numbers up to 10.

Coordination number 2: They are uncommon and generally restricted to Cu(I), Ag(I),
Au(I), and Hg(II) and all are d10 ions e.g. [CuCl2]-, [Ag(NH3)2]2+, [Au(CN)2]-, Hg(CN)2.
The shape is LINEAR.

L M L

Coordination number 3: Their shape is TRIGONAL PLANAR e.g. [Cu(CN)3]2-, [HgI3]-

M
L L

Coordination number 4: The shape is usually TETRAHEDRAL or SQUARE


PLANAR but the tetrahedral is more common e.g. [CoCl4]2-, [MnCl4]2- -tetrahedral
geometry, [PdCl4]2-, [AuCl4]- [PtCl4]2- square planar.
L
L L
L
M M
L
L L
L Square Planar
Tetrahedral
Coordination number 5: The usual shape is TRIGONAL BIPYRAMID or SQUARE
BASED PYRAMID. For example, [CdCl5]3-, [CuCl5]3- - trigonal bipyramid, [WCl4O]-,
[TcCl4N]- - square based pyramid.
L
L
L
L L
L M
M
L L L
L
Trigonal bipyramidal Square-based pyramid

Coordination number 6: This is another common coordination number. There shapes


are usually OCTAHEDRAL or TRIGONAL PRISM. For example, [TiF6]2-,
[Ti(OH2)6]3+, [Co(OH2)6]2+ - octahedral, [Zr(CH3)6]2- - trigonal prism
L
L
L
L
L L
M
M L
L
L L
L
L Trigonal prism
Octahedral

In octahedral complexes the 4 ligands (in black) that lie in the plane are the equatorial
ligands and the two that are above and below the plane (in red) are axial ligands. The
most commonly studied complexes are the octahedral, square planar and tetrahedral
complexes

(B) TYPES OF LIGAND


Monodentate Ligands: these are ligands that use only I pair of electrons to bond to the
central metal, for example H2O, NH3, Cl- etc.

Ambidientate Ligands: are monodentate ligands that can bond to the central atom
through either of the two or more donor atoms e.g. NO2– it can bond through the
oxygen (ONO- nitrito) or through the nitrogen (NO2 nitro). Another example is CSN-
. This can bond through the Nitrogen (NCS- isothiocyanate) or through the sulphur
(SCN- thiocyanate).

Polydentate Ligands: These ligands donate two or more pairs of electrons from
different atoms in the ligand and to different sites in the structure of the complex. The
specific names of such ligands are based on the number of donating sites. Below are
few examples

a. Bidentate Ligands: the ligands donate two pairs of electrons e.g. ethylenediamine
H2NCH2CH2NH2, oxalate ion -O2C-CO2-.

b. Tridentate Ligand: 3 pair of electrons e.g. diethylenetriamine


H2NCH2CH2NHCH2CH2NH2

c. Tetradentate Ligand: Porphyrin

d. Hexadentate Ligand: 6 pairs of electron e.g. ethylenediaminetetraacetate ion


(EDTA) [(-OOCCH2)2NCH2CH2N(CH2COO-)2]4-

Chelating Ligands: When a ligand attaches to the same central metal by two or more
atoms forming a ring structure. The complex formed is called a chelate. Chelating
ligands increase the stability of the complex.
UNIT FOUR - Isomerism in coordination compounds

Isomerism

Structural Isomerism Stereoisomerism

 Ionization Isomerism  Geometrical Isomerism


 Hydration Isomerism  Optical Isomerism
 Coordination Isomerism
 Linkage Isomerism
 Polymerization Isomerism

Ionization Isomer: This occurs when there is an interchange of an anionic ligand that
is inside the coordination sphere with another anionic ligand outside the coordination
sphere e.g.
 [Co(NH3)5Br]SO4 (violet in colour)
 [Co(NH3)5SO4]Br (red in colour)

Hydration Isomer: This arises when there is an interchange of H2O and another ligand
between the coordination sphere and outside of it e.g.
 [Cr(H2O)4Cl2]Cl•2H2O – Green
 [Cr(H2O)5Cl]Cl2•H2O – Blue green
 [Cr(H2O)6] Cl3 – Violet

Coordination Isomer: These isomers are formed from the interchange of ligand
between 2 different metal centers and can only happen if the salts which form the cation
and anions are themselves complex ions e.g.
 [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
 [Co(NH3)6] [Co(NO2)6] and [Co(NH3)4(NO2)2] [Co(NH3)2 (NO2)4]
Linkage Isomer: this arises when one or more ligands can coordinate to a metal ion in
more than one way e.g.
 [Co(NH3)5(CSN)]Cl2 coordination can occur through S – atom or N – atom of
the CSN ligand
Co–NCS Isothiocyanate
Co–SCN Thiocyanate
 [Co(NH3)5(NO2)] Cl2 coordination can occur through O – atom or N – atom of
the NO2 ligand
Co–ONO Nitrito
Co–NO2 Nitro

Polymerization Isomer: These isomers have the same empirical formulae but different
molecular masses e.g.
 [Pt(NH3)2(Cl)2] (PtnN2nH6Cl2n) {n =1}
 [Pt(NH3)4] [Pt (Cl)4] (PtnN2nH6Cl2n) {n =2}

Geometrical Isomer: They have the same molecular formulae but different arrangement
of their ligands in space. For coordination complexes there are two kinds.
a. Cis-Trans isomerism: here is the spatial arrangement of only 2 of the ligand
especially in square planar and octahedral complexes.
 For the cis- isomer the two ligands are at 90° to each other with respect
to the central atom and so the bond angle between the 2 ligands is 90°.
 Trans- isomers have the 2 ligands at 180° to each other i.e. opposite each
other.
L1 L2 L2 L1
L1 L1 L2 L1 L2 L1 L1 L2 L2 L2

L2 M L2 L2 M L1 M M M M

L1 L2 L2 L2 L2 L1 L2 L1 L2 L2
L2 L2 L2 L1
Trans - isomer Cis - isomer
(a) (b) (c) (d)
Square planar complexes Cis - isomer Trans - isomer
M - central metal Octahedral complexes
L1 and L2 are different ligands
Using L1 as reference point
90o - represented in red
180o - represented in blue
b. Mer-Fac isomerism: here the spatial arrangement involves only 3 of the ligands
and occurs in only octahedral complexes. For the fac- isomer the 3 ligands are at
90° to each other. For the mer- isomer 2 of the ligand would be at 90° to each
other while the third one will be at 180° to one of the other 2.
L1 L1
L2 L1 L2 L2

M M

L1 L2 L1 L1
L2 L2
mer - fac-
M - central metal
L1 and L2 are different ligands
Using L1 as reference point
90o - represented in red
180o - represented in blue

Optical Isomers: these are two complexes that are mirror images of each other. When
these mirror images are not superimposable they are called enantiomers and if they are
superimposable they are called diastereomer.
The mirror images can be distinguished by the direction they rotate in the presence of
polarized light. The one that rotate towards the left direction is called Laevorotatory (l
or -) and other will rotate toward the right called Dextrorotatory (d or +). The degree
of rotation of enantiomers will be the same but in opposite direction (left and right)
hence are optically active.
While for diasteromers they would move in the same direction and therefore optically
inactive. So if [Co(NH3)4(Cl)2] is an enantiomer and have a degree of rotation of 24°,
the one that rotate towards the left would be labeled as (l)-[Co(NH3)4(Cl)2] or (-)-
[Co(NH3)4(Cl)2] and the one that rotate right would be labeled as (d)-[Co(NH3)4(Cl)2]
or (+)-[Co(NH3)4(Cl)2]

NH3 Cl Cl
NH3
Cl NH3 H3N NH3 H3N NH3
H3N Cl
Co Co Co Co
Cl H3N H3N NH3
H3N Cl NH3 NH3
NH3 NH3 Cl Cl

These are non-superimposable mirror image These are superimposable mirror image
hence they are optically active and are therefore are not optically active and are
enantiomers diastereomers
For octahedral chelating ligand containing 3 equivalent ligands the prefix would be Δ
(delta) right handedness and Λ (lamda) for left handedness.

3+ 3+

Co Co

L-[Co(en)3]3+ D-[Co(en)3]3+

R and S prefixes is the convention for labelling tetrahedral complexes with four
different groups attached. The four groups attached to metal atom are prioritized
according to the atomic number of the attached atoms, highest priority being assigned
to highest atomic number and the one with the lowest atomic number has the lowest
priority and it is ignored. Here the atoms attached directly to the metal (Cu) are Br (35),
Cl (17), O (8) and C (6). These atoms have been labelled 1 to 4 from highest to lowest.
In ‘a’ moving from 1 to 3 is anticlockwise and in ‘b’ it is clockwise. The R- and S-labels
for the enantiomers refer to a clockwise (rectus) and anticlockwise (sinister) moving
from high to low priority:

a b

3 3
H2O H2O

2–
2– Cu
Cu Br
CN NC 1
Br 4 4
1 Cl
Cl 2
2

S- R-
UNIT FIVE – Crystal Field Theory (CFT)

This is one of the theories used to explain the bonding in Transition metal complexes.
Most of what has been discussed above is based on another theory, which is the Valence
Bond theory (VBT). VBT describes the bond between the metal and the ligand as
coordinate bond, where the ligand donates loan pair(s) of electrons to the vacant d or f
orbital of the metal.

In CFT the bond described to be purely electrostatic. Here the metal being positively
charged is attracts the ligands which are negatively charged spheres. Ligands of course
are usually ions (Cl-, Br- etc) but for neutral ligands like ammonia or water, they dipoles.
N and O are more electronegative that H and would draw the electron they share more
towards themselves giving them a partial –ve charge (-δ) and the H would have a partial
+ve charge (+δ). The –ve charged portion would now be attracted to the central metal
(which is a cation).
A. Before the ligands approach the metal the d-orbitals are degenerate (i.e. equal
in energy).
B. Although the electrons of the ligands are attracted to the central ion but as the
ligands approach closer to the metal ion there is also repulsion between the
electrons in d-orbitals and the electrons of the ligands.
C. This effect raises the energy of the d-orbital and consequently split them. The
direction of approach of the ligand to the d-orbitals affect the type of splitting
that occurs.

eg
t2
Energy

D
(B)
D
(A) As the ligands get t2g e
(C)
d-orbitals are closer to the
d-orbitals, the energy On getting even Tetrahedral Complex
degenerate as the
ligands are still far of d-orbitals is eaised, closer the ligands
from it. the remain cause the d-orbitals
degenerate. to split

Octahedral Complex
The magnitude (size) of ∆ depends on the strength of the ligands. Ligands that result
in large values of ∆ are referred to as strong field ligands and those that result in small
values of ∆ are called weak field ligands. The arrangement of ligands according to their
field strength is called the spectrochemical series

𝐼 − < 𝐵𝑟 − < [𝑁𝐶𝑆]− < 𝐶𝑙 − < 𝐹 − < [𝑂𝐻]− < [𝑜𝑥]2− ≈ 𝐻2 𝑂 < [𝑁𝐶𝑆]− < 𝑁𝐻3 < 𝑒𝑛 < 𝑏𝑝𝑦 < 𝑝ℎ𝑒𝑛 < [𝐶𝑁]− ≈ 𝐶𝑂

Weak field ligands Strong field ligands

An increase in the crystal field splitting would result in force the electrons to pair. Strong
field ligands force pairing because they cause the crystal field to split very wide such the
electrons cannot move into 𝑒𝑔 -orbitals and would rather be forced to pair in the 𝑡2𝑔 .
The same is applicable in a tetrahedral environment only this time instead of ∆𝑜𝑐𝑡 ; ∆𝑡𝑒𝑡
would be used. (Remember to reverse the orbitals i.e. e comes down and t2 goes up).

eg
eg
Doct Doct
Energy

t2g
t2g
[Fe(H2O)6]2+
[Fe(CN)6]4-

Coordination compound apart from being coloured they exhibit magnetic properties
such as being diamagnetic (no unpaired electrons) or paramagnetic (one or more
unpaired electrons). In the presence of weak field ligands the complex is said to have
high spin however due to effect of strong field ligands which then forces pairing the
complex is described as being low spin.

Jahn-Teller Distortion
Sometimes an octahedral complex undergoes distortion in its shape. This distortion can
take place either by the elongation of the axial ligands or the compression of equatorial
ligands.
L

L L
L L L L
L L
M Elongantion of axial ligands M Compression of equotorial ligands M

L L L L L
L
L L
Regular octahedral complex
L Distored complex
Distored complex

This distortion is a manifestation of the Jahn-Teller effect and its referred to as


tetragonal distortion. This effect occurs when the ground electronic configuration is
asymmetrically filled making the geometry unstable and in order to bring about stability
the distortion occurs. A common example is d9 complexes of Cu(II).

dx2-y2

dz2
dx2-y2 dz2
Energy

dxy
dxy dyz dxz
Regular octahedral complex
dyz dxz
Jahn-Teller distortion

The asymetrical filling of the eg orbital caused the distortion

Lability and Inertness


Any metal complex that’s undergoes reactions with t 1 ≤ 1 min at ordinary conditions
2
(room temperature and about 0.1 M solution) is described as being kinetically labile. If
the reaction takes significantly longer than this, the complex is kinetically inert. For
example, iron(II) chloride was dissolved in water gives green solution on addition of
few drops of cyanide solution it changes to purple. If conc NH3 is added or water, there
will be no change in the colour of the solution. This is because the cyano complex is
inert and the aqou complex is labile.
1. If the crystal field splitting is wide an incoming ligand will not be able to
substitute it such a complex is inert.
2. Very small ions are often less labile because they have greater M-L bond energy
and it becomes sterically difficult for incoming ligands to approach the metal ion
3. chelating ligand cause inertness
4. d10 ion of Zn2+, Cd2+ and Hg2+ are very labile
5. Across the 3d period, M2+ ions are labile and Cu2+ is most labile due to
distortions.
6. d-metal complexes with d3 and low-spin d6 configuration like Cr3+, Fe2+ and Co3+
are inert
7. High charge and small size results in inertness.
8. The more filled the d-orbitals the more labile.

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