COORDINATION CHEMISTRY

DOUBLE SALT COORDINATE COMPOUND

❖Ionize into all ❖ionize into complex ion and normal ion
constituent ions completely never complete ionization

❖FeSO4. (NH4)2SO4.6H20 ❖K4[FeCN6]

Mohr’s Salt Potassium ferrocyanide

Ionization of K4[FeCN6]
❖Coordination entity [FeCN6]4-
❖Central metal ion Fe
❖Ligand CN [neutral, ambidentate]
❖Donor atom C
❖Coordination number of central metal atom 6

❖Counter ion 4[K+]

TYPES OF LIGANDS
UNIDENTATE ligand containing single donor atom

H2O, NH3, CN-

BIDENTATE ligand containing two donor atoms

Ethylenediamine(en), oxalate →
POLYDENTATE ligand containing more than two donor atoms
EDTA (ethylene diamine tetra acetate)→ 6 donor atoms
Hexadentate ligand
AMBIDENTATE ligands containing 2 donor atoms either (one) of which can
donate at one time

NO3-, SCN-
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CHELATES- An inorganic metal complex containing ligand bonded to central
metal atom at 2 or more points- EDTA
WERNER’S COORDINATION THEORY
A metal shows two types of valencies primary & secondary.
PRIMARY VALENCY SECONDARY VALENCY
❖Ionizable ❖non ionizable
❖Equal to positive charge ❖equal to number of ligands
on the metal atom present in coordination sphere
❖or oxidation state ❖or coordination number
❖satisfied by negatively ❖satisfied by positive, negative or
charged ligands neutral ligands
normal lines dotted lines
Secondary valency of a metal determines geometry of the complex
compound
Common geometry- octahedral, square planar, tetrahedral.
DRAWBACKS could not explain the directional nature of bonds
Could not explain magnetic & optical properties of complex
compounds
HOMOLEPTIC COMPLEXES HETEROLEPTIC COMPLEXES
❖Complexes with same ❖Complexes with different
kind of ligands kind of ligands
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IONIZATION OF COORDINATE COMPOUNDS ON THE BASIS OF WERNER’S

THEORY
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ISOMERIZATION FOUND IN COORDINATION COMPOUNDS

STUCTURAL ISOMERISM same molecular formula different structure
Ex- cis- trans

SOLVATE ISOMERISM same molecular composition but differ in

number of water molecules present as ligands
This is also known as hydrate isomerism.
Ex- CoCl3.6H2O
[Co (H2O)6] Cl3 [Co(H20)5Cl] Cl2.H2O
VIOLET DARK GREEN
[Co (H2O)4(Cl)2] Cl.2H2O
GREEN
IONIZATION ISOMERISM compounds which give different ions in
solution although they have the same composition
Ex- [Co (NH3)5Br]SO4 & [Co (NH3)5 SO4] Br
LINKAGE ISOMERISM when more than one atom in a monodentate
ligand may function as a donor atom (ambidentate
ligand)
Ex- [Co (NH3)5[ ONO] Cl2 & [Co (NH3)5[ NO2] Cl2
Donor atom O Donor atom N
COORDINATION ISOMERISM found in those complex compounds which
contain both cationic and anionic complexes and
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isomers differ wrt distribution of ligand within
complexes
Ex- [Co (NH3)6] [Cr(C2O4)3] & [Co(C2O4)3] [Cr (NH3)6]
STEREO ISOMERISM different arrangement in space but same molecular
formula
Two types of stereoisomerism are seen: geometrical, optical
GEOMETRICAL ISOMERISM heteroleptic complexes show this isomerism
CN mainly being 4 or 6
[MA2B2] TYPE [CoCl2(en)2] exists in cis and trans form
A= monodentate, B= bidentate

Cis trans
[MABCD] TYPE all unidentate [Pt (Cl)(Py)(Br)(NH3)]

[MA4] means tetrahedral complex cis, trans not possible

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[MA2B4] [Co (NH3)4(Cl)4] octahedral complexes

[MX2(L-L)2] [Co(ox)2(Cl)2]
X= monodentate, L= bidentate

[MA3B3] octahedral complexes [Co (NH3)3(NO2)2]

OPTICAL ISOMERISM octahedral complexes with CN=6.

If such octahedral complexes have bi or tridentate ligands the compound will
show optical isomerism.
Both d and l forms are non-superimposable hence enantiomers
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Dextrorotatory(d) laevorotatory(l)
Rotate plane of Rotate plane of
polarized light in polarized light in
clock wise direction anti- clock wise direction
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 COORDINATION CHEMISTRY

RULES FOR IUPAC NOMENCLATURE OF COORDINATE COMPOUNDS

Anionic ligands whose name ends with -ide are named by replacing
-ide with -o
Anionic ligands whose name ends with -ite or -ate become -ito or -
ato
Neutral ligands are named as it is, ligands carrying positive charge
are named as -ium
Prefixes like mono, di, tri etc is used to indicate number
Positive and neutral complexes have no special ending but anionic
complexes end in suffix -ate
Oxidation number is indicated in roman numeral inside square
brackets
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Full name should not contain any gaps for ligands which act as a
bridge between two metal atoms, the Greek letter mu is written
before their names
Common geometries of complex compounds

OUTER ORBITAL COMPLEXES complexes that involve hybridization of outer

orbitals (nd subshell). Ex- sp3d, sp3d2
Also, k/as HIGH SPIN COMPLEXES They are formed when weak field ligands
approach central metal atom.
INNER ORBITAL COMPLEXES complexes that involve hybridization of inner
orbitals[(n-1) d subshell]. Ex- dsp2, d2sp3
Also, k/as LOW SPIN COMPLEXES They are formed when strong field
ligands approach central metal atom.

Magnetic properties due to the presence of unpaired electrons

paramagnetism is seen, fully filled electronic configurations will be
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diamagnetic. MAGNETIC MOMENT =√𝒏(𝒏 + 𝟐), where n= number of
unpaired electrons. UNIT is bohr magneton.

VALENCE BOND THEORY[VBT]

The central metal atom makes available empty orbitals for formation of
coordinate bonds with suitable ligands.
This is done by hybridization of atomic orbitals. These hybrid orbitals are
described according to the geometry of the complex. Each ligand has at least
one orbital to donate lone pair of electrons.
The number of empty orbitals available gives the coordination number of the
central metal atom.
OUTER ORBITAL & INNER ORBITAL COMPLEXES are formed.
Complex which contain all paired electrons are repelled by magnetic field:
DIAMAGNETIC
Complex which contain un-paired electrons are attracted by magnetic field:
PARAMAGNETIC
LIMITATIONS OF VBT
1 cannot explain detailed magnetic properties of complex compounds
2 cannot explain the optical absorption spectra of coordination
compounds
3 no information on thermodynamic stability of coordination
compounds
4 fails to make distinction between strong and weak field ligands
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 COORDINATION CHEMISTRY

CRYSTAL FIELD THEORY[CFT]

POSTULATES
Ligands are point charges and bonded to metal atoms by electrostatic
attraction. This is a theoretical assumption.
The splitting of degenerate d orbitals under the influence of approaching
ligands into different energy sets is called crystal field splitting
This plays an important role in explaining the geometry and characteristics of
coordinate complexes or entities
The three d orbitals with lower energy are called t2g orbitals
While the two d orbitals with higher energy are termed as eg orbitals
The difference in energy between the two groups of orbitals is called CFSE
Or CRYSTAL FIELD SPLITTING ENERGY
SPECTROCHEMICAL SERIES
I-<Br-<S2-<SCN- <Cl- <F- <OH- <C2O42- <O2- <H2O <NCS- <NH3 <en <NO2-
<CN- <CO
Strong field ligands cause large splitting hence form low spin complexes
Weak field ligands cause small splitting hence form high spin complexes

FOR TETRAHEDRAL COMPLEXES

t2g>eg; t2g has greater energy than eg
the energy is so small in this case that is not sufficient for pairing of electrons
FOR OCTAHEDRAL COMPLEXES
eg> t2g; eg has greater energy than t2g
the energy, in this case that is sufficient for pairing of electrons

𝛥0 = 𝐶𝐹𝑆𝐸
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𝛥′ 𝑜𝑟 𝑃 = 𝑒𝑛𝑒𝑟𝑔𝑦 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑡𝑜 𝑜𝑣𝑒𝑟𝑐𝑜𝑚𝑒
𝑟𝑒𝑝𝑢𝑙𝑠𝑖𝑜𝑛 𝑑𝑢𝑒 𝑡𝑜 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 𝑝𝑎𝑖𝑟𝑖𝑛𝑔

𝛥0 << 𝛥′ ℎ𝑖𝑔ℎ 𝑠𝑝𝑖𝑛 𝑐𝑜𝑚𝑝𝑙𝑒𝑥, 𝑤𝑒𝑎𝑘 𝑓𝑖𝑒𝑙𝑑 𝑙𝑖𝑔𝑎𝑛𝑑𝑠

FOR TETRAHEDRAL COMPLEXES

𝛥0 ≫ 𝛥′ 𝑙𝑜𝑤 𝑠𝑝𝑖𝑛 𝑐𝑜𝑚𝑝𝑙𝑒𝑥, 𝑠𝑡𝑟𝑜𝑛𝑔 𝑓𝑖𝑒𝑙𝑑 𝑙𝑖𝑔𝑎𝑛𝑑𝑠

FOR OCTAHEDRAL COMPLEXEs

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FACTORS INFLUENCING ORBITAL SPLITTING ENERGY
Oxidation state of metal ion greater charge more is the CFSE
Geometry nature of ligand
Dissociation constant is reciprocal of stability constant