Module 3
Module 3
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.
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
M
L L
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
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-.
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
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
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
dx2-y2
dz2
dx2-y2 dz2
Energy
dxy
dxy dyz dxz
Regular octahedral complex
dyz dxz
Jahn-Teller distortion