COORDINATION COMPOUNDS

1. COORDINATION COMPOUNDS AND DOUBLE SALTS:

Double Salts Coordination Compounds or Complex salts

 Double salts are compounds composed of  Coordination compounds are complex

 Ex: KCl.MgCl2⋅6H2O.--- Carnallite.

more than one type cations and an anion compounds containing central metal atoms or
ions bonded to electron-rich molecules or
CaCO3.MgCO3 ----- Dolomite ions known as ligands, via coordinate covalent
K2SO4.Al2(SO4)3.24H2O -–Potash alum bonds.
 Ex: [Cu(H2O)4]SO4. H2O
 A double salt is prepared by evaporating an  A coordination compound is prepared
aqueous solution containing of two simple evaporating an aqueous solution containing
salts in 1:1 molar ratio. two simple salts/ compounds not necessarily
Ex: (NH4)2SO4 aq. + FeSO4 aq in 1:1 molar ratio.
↓∆ Ex: FeSO4 aq. + 6NH3 aq
(NH4)2SO4 FeSO4 6H2O (solid) ↓∆
[Fe(NH3)6]SO4 (solid)
Consists two types of cations of one type of Consists of one complex cation and simple anion
anion. i.e. complex cation and simple anion.
 When double salts are dissolved in water,  When complex salts are dissolved in water,
they produce the same simple ions as the they do not produce the same ions as the
simple salts from which they are prepared. simple salts from which they are prepared.
(NH4)2SO4 FeSO4 6H2O Water
→
Fe+2+ 2NH4+1 The produce at least one complex ion in
solution.
+ 2 SO4-2.
[Fe (NH3)6]SO4 Water
→
[Fe(NH3)6]+2 + SO4-2.
 Simple ions produced by the double salts  Complex ions do not give positive tests for
answer the regular confirmatory tests for regular confirmatory tests of simple ions.
these ions.
Ex: [Fe (NH3)6]SO4 when dissolved in water
Ex: (NH4)2SO4 FeSO4 6H2O when dissolved in does not answer tests for Fe+2 and NH3
water answers tests for Fe+2 ions, NH4 +1 ions separately. Instead it answers tests for
and SO4-2 ions. [Fe(NH3)6]+2 ions and SO4-2 ions.

2. TYPES OF COORDINATE COMPOUNDS:

Cationic complexes Anionic complexes Neutral complexes
Form positively charged complex Form negatively charged complex Complex carries no net
ions aqueous solution. ions in aqueous solution. charge and do not form
any ions in aqueous
solution.
Ex: [Ag(NH3)2]Cl →[Ag(NH3)2]+1 + Cl-1 Ex: K4[Fe (CN)6] →4 K+1 +[Fe(CN)6] -4 Ex: [Ni(CO)4],
[Co(NH3)3Cl3]
 1. BONDING IN COORDINATION COMPOUNDS:
(i) Werner`s Theory of Bonding:
Central metal atom in a complex ion or molecule exhibits two types of valencies; Primary
valency and Secondary valency.

Primary Valency Secondary Valency

Represents the oxidation state of the central metal Represents the total number of coordinate bonds
atom or ion in the complex. between the CMA/CMI and ligands in the
complex.
Known as ionisable valency. Known as non-ionisable valency.
Always satisfied by negative ions. Always satisfied by ligands which can be neutral
molecules/-ve ions/+ve ions.
Non directional in nature. Do not define the Directional in nature. Give rise to the unique
geometry of the complex. geometry of the complex.

* A negative ion can satisfy both primary and secondary valancies. If a negative ion satisfies both the valencies
then it does not become free ion when dissolved in water.

Werner’s presentation the coordination compound CoCl3 6NH3. Dotted lines indicate primary valencies, and solid
lines secondary valencies.

* How to find the primary and secondary valencies when the molecular formula of a complex is
known?
Ans: Dissolve the salt in water and treat the solution with suitable reagents to identify the type and number of
ionisable valencies. Non ionisable valencies do not answer the test for simple ions.

Mol. Formula. CoCl36NH3 CoCl3 3NH3

Reagent added to
the aqueous AgNO3
solution
No. of moles of ppt. Three moles of AgCl ppt. Zero moles of AgCl ppt.
formed
No of ionisable Three Zero
valencies and
structure of the
complex.
 (ii) VALENCE BOND THEORY: (FOR C N =4 AND C N=6)

* Metal-ligand bonds are regarded as coordinate covalent bonds in which electron pairs from the donating ligand

enter vacant orbitals of the central metal atom/ion.

* Hybridisation of atomic orbitals of CMA/CMI:

 Before bonding with the ligands, empty orbitals of nearly equivalent energy from the CMA/CMI, mix
with each other to produces orbitals of equal energy.
 The type of hybridisation depends upon the C N and geometry of the complex.

Coordination Geometry of the Hybridisation & Examples:

No. complex with bond (No. of hybrid
angles. orbitals)
2 Linear ---- 1800 sp
(2)

3 Trigonal planar-- 1200 sp2

(3)

4 Tetrahedral ----109.50 sp3 or dsp2

or square planar--- 900 (4)

5 Trigonal bipyramidal--- d sp3

1200 between (5)
equatorial bonds & 900
b/n axial and equatorial
bonds
ex: [Fe(CO)5]
 6 Octahedral -----900 sp3d2 or d2sp3
(6)

[Mn(H2O)6]SO4

 The empty hybrid orbitals of CMI/CMA then overlap with the fully filled orbitals of ligands to form
coordinate bonds.
 During hybridisation, CMA/CMI can use empty orbitals of valence shell as well as that of penultimate
(n-1) shell.
Ex: If central metal ion is Cr+3, then it can use 3d, 4s, 4p and 4d orbitals for hybridisation.
 If only valence shell orbitals are involved in hybridisation then the complex is known as Outer Orbital
Complex and if valence shell and (n-1) th shell orbitals are involved in hybridisation, complex is called
Inner Orbital Complex.
* Magnetic property of the complex: After the hybridisation of the CMI/CMA if (n-1) d orbital consists of
unpaired electrons then the complex is paramagnetic and if it is zero then the complex is diamagnetic in
nature. Spin only magnetic moment = √ n(n+ 2) , where n= number of unpaired electrons in the penultimate
shell of CMA /CMI after hybridisation.
 Low spin complex: (n-1) d orbital of CMA/CMI contains 0,1,2 unpaired electrons after hybridisation.
 High spin complex: (n-1) d orbital of CMA/CMI contains 3,4,5 unpaired electrons after hybridisation

* List of ligands in the increasing order of their Strengths:

I− < Br− < S2− < SCN− < Cl− < F− < OH− < C2O42− <O-2< H2O <NCS− < NH3 < en <NO2−<
CN− < CO

NOTE: Ligands from I-1 to H2O are weak filed ligands and NCS− to CO are strong field ligands.

* C N=6 (OCTAHEDRAL COMPLEXES of d block elements): General electronic configuration of d block elements
is [Rare gas] (n-1)d1-10 ns1-2
CMA/CMI can undergo sp3d2 or d2sp3 hybridisation
Complexes have octahedral geometry.
The type of hybridisation depends upon the electronic configuration of the (n-1) d orbital of the metal
ion/atom and strength of the ligands.
 If central metal atom or ion has (n-1) d0 to (n-1) d3 configuration, then CMA/CMI undergoes
d2sp3hybridisation.
 If central metal atom or ion has (n-1) d7 to (n-1) d10 configuration then, CMA/CMI
sp3 d2hybridisation.
 If central metal atom or ion has (n-1) d4 to (n-1) d6 configuration then nature of hybridisation
depends upon the strength of ligands.
 Under the influence of strong filed ligands, the electrons of (n-1) d orbitals are forced to pair
up against Hund`s rule, to make two orbitals empty. Then the metal ion/atom undergoes
d2sp3 hybridisation.
 Under the influence of weak filed ligands, no pairing up of electrons takes place in (n-1) d
orbitals. Metal uses ONLY valence shell orbitals to forms sp 3d2 orbitals.
 SOME EXAMPLES OF HYBRIDISATION IN OCTAHEDRAL COMPLEXES
(a) VBT applied to [FeF6]-3. hexafluoridoferrate(III) ion

Electronic configuration of Fe & [18 e-1] 3d64s2

CMA/CMI [Ar]3d5,4s0

Outer orbital of CMA/CMI

Nature of the ligand Weak field ligand. No pairing of electrons in 3d orbitals. Hence
metal ion undergoes sp3d2 hybridisation.
Outer orbital of CMA/CMI in
presence of ligand and
hybridisation.

Bonding between hybridised

orbitals of CMA/CMI & ligands
↑↑ ↑ ↑ ↑ ↑

F F F F F F
Inner or outer orbital complex Outer orbital complex
Magnetic property and spin only Paramagnetic. μ =√ n(n+ 2) =√ 35 BM
magnetic momentum. High spin complex.

(b) VBT applied to [Fe (CN)6]-3 ---- hexacyanoferrate (III) ion

©[Cr(H2O)6]Cl3 - hexaaquachromiun(III) Chloride & [Cr(en)3]Cl3 -tris(ethane-1,2-diamine)chromium(III) Chloride

Electronic configuration [18 e-1] 3d54s1 & [Ar]3d3,4s0

of Cr (24) and Cr+3 (21)
Outer orbital of 3d 4s 4
CMA/CMI

Nature of the ligands H2O is a weak ligand and (en) strong ligand. Since two 3d orbitals are already
empty, pairing up of electrons is not needed in case of (en) ligands.
Outer orbital of
CMA/CMI in presence of
ligand and hybridisation.
Hybridised orbital of
CMA/CMI in the complex --[Cr(H2O)6]+3
and bonding with ligands ↑ ↑ ↑ ↑ ↑↑

H 2O H 2O H 2O H 2O H 2O H 2O
&

--- [Cr(en)3]+3
↑ ↑ ↑ ↑ ↑↑
en en en
Inner or outer orbital Inner orbital complex
complex
Magnetic property and Paramagnetic. n=3,
spin only magnetic μ =√ n(n+ 2) =√ 15 BM
momentum.

Structure of the complex

Example: [Co(ox)3]-3 ---- trioxalatocobaltate (III) ion

Electronic configuration of Co & [18 e-1] 3d74s2

Co+3 ion [Ar]3d5,4s0

Outer orbital of CMA/CMI

Nature of the ligand Weak field ligand. Pairing up of electrons in 3d orbitals takes
place since (ox)-2 is a chelating ligand. Hence metal ion
undergoes sp3d2 hybridisation.
Outer orbital of CMA/CMI in
presence of ligand and
hybridisation.
 Bonding between hybridised
orbitals of CMA/CMI & ligands

Type equation here .

Inner or outer orbital complex Inner orbital complex
Magnetic property and spin only Diamagnetic, μ =√ n(n+ 2) = 0
magnetic momentum. Low spin complex.

Paramagnetic substances: Compounds / atoms/ions which are attracted to magnetic fields.

Paramagnetic compounds have unpaired electrons.
Diamagnetic Substances: Compounds/ atoms/ions which are repelled from magnetic fields.
Diamagnetic compounds have no unpaired electrons.

 C N=4 (TETREAHEDRAL AND SQUARE PLANAR COMPLEXES of d block elements):

CMA/CMI can undergo sp3 or dsp2 hybridisation
Complexes have tetrahedral (sp3) or square planar (dsp2) geometry
The type of hybridisation depends upon the electronic configuration of the (n-1) d orbital of the metal
ion/atom and strength of the ligands.
 If central metal atom or ion has (n-1) d0 & (n-1) d10configuration then CMA/CMI undergoes
sp3hybridisation.
ex: Mn in MnO4-1 and MnO4-2, Cr in Cr2O7 -2 and CrO4-2, Zn in [Zn (NH3)4] +2 are sp3 hybridised as their
3d orbitals have zero electrons (Mn and Cr) and 10 electrons respectively.
 If central metal atom or ion has (n-1) d5, (n-1) d6 and (n-1) d8 configurations of first series (3d series)
of transition elements, then CMA/CMI undergoes dsp2 hybridisation in presence of strong ligands
and sp3 hybridisation in presence of weak ligands.
 In case of Pt+2 and Pd+2 with 5d8 and 4d8 configurations hybridisation is always dsp2 whether the
ligand is strong or weak.

EXAMPLES OF TETRAHEDRAL AND SQUARE PLANAR COMPLEXES, (C N=4)

(1) [Ni(CO)4] ----- tetracabronylnickel(0). Electronic configuration of Ni – [Ar]3d 84s2. CO is a strong ligand. Hence
4s electrons are paired up in 3d orbitals before the hybridisation (sp 3). Complex is diamagnetic since n= 0 in the
3d orbital of the metal in the complex.
(2) [Ni(CN)4]-2 -----tetracyanonickelate(II) ion. Configuration of Ni +2 --- [Ar]3d8

CN-1 is a strong ligand. Hence electron paring takes place in 3d to make one orbital empty
and Ni+2 undergoes dsp2 hybridisation. Since the no. of unpaired electron in 3d orbital after
hybridisation is zero, complex is diamagnetic.

3) [Ni(Cl)4]-2 ----- terachloridonickalate(II) ion.

Configuration of Ni ---[Ar]3d8 4s2 and Ni+2 --- [Ar]3d8
Cl-1 is a weak ligand. Therefore, no pairing up of electrons in the 3d orbital takes place. Ni +2 under goes sp3
hybridisation.
No. of unpaired electrons in 3d after hybridisation=2. Therefore, complex is paramagnetic, μ =√ 8 BM.

(4) K2 [ Mn (Br)4]—Potassium tetrabromidomanganate(II).

Configurations of Mn(25e) –[Ar]3d54s2 and Mn+2 --- [Ar]3d5.
Br is a weak ligand. Hence no pairing of electrons in 3d orbitals takes place and Mn +2 undergoes sp3
-1

hybridisation. No. of unpaired electrons in 3d after hybridisation= 5. Therefore, complex is paramagnetic with, μ
=√ 35 BM.
ANSWER THE FOLLOWING QUESTIONS.
(5) Predict the hybridisation of central metal atoms/ions in the following complex and
calculate their μ. Also write the IUPAC names of these complexes.
(a) (NH4)2 [CoF4] (b) [Pt (NH3)4]+2(c) [FeBr4]-1 (d) Mg[Co(NH3)(NO2)5].
(6) Predict the hybridisation of central metal ion in the following complexes.
(a) Atomic number of central ions is 29 and oxidation number= +2. No. of sec.
valencies= 4, μ=1.73 BM
(b) Atomic number of central metal ion=25 and oxidation number= +2, No of
ligands =6. μ=5.92 BM
____________________________________________________________________________________

CRYSTAL FIELD THEORY (CFT)

 The ligands are treated as point charges. The interactions between CMA/CMI & ligands are purely
electrostatic in nature. i.e it can be ion-ion interactions like ionic compounds or ion -dipole interactions.
 When the ligand approach or interact with CMA/CMI they position themselves in 3D space in definite
directions to keep maximum separation between them. This creates a -ve field around the CMA/CMI known
crystal filed. (Analogous to the -ve or +ve fields surrounding the ions in ionic crystals)
 When the ligands approach the CMA/CMI, they interact with their `d` orbitals. This interaction increases
the energy of electrons in the d subshell due to repulsion between them and electrons of ligands.

 Crystal filed splitting: Since the five d orbitals have different spatial orientations, the approaching ligands do
not interact with these orbitals equally. Hence the d orbitals do not experience same repulsive forces. Due
to this, in the complex, degeneracy of the d orbitals vanishes (is lifted), which results in splitting of d orbitals
into two sets, with different energies; (i) d z & d x − y (ii) dxy, dyz & dzx. This is known as crystal filed splitting.
2 2 2

 Note that two sets of d orbitals are along the axes. (d z and d x − y ) and remaining three sets of
2 2 2

orbitals are in XY, YZ and ZX planes. ( dxy, dyz and dzx)

 Crystal Field Splitting Energy (CFSE): The difference in the energies of two sets of d orbitals of CMA/CMI in
the complex. It depends upon the extent of splitting (i.e. the gap between the two sets of d orbitals)

 Extent of splitting of d orbitals depends upon the following factors

(i) The nature of the ligands. The stronger the ligand, the greater is the splitting.
I− < Br− < S2− < SCN− < Cl− < F− < OH− < C2O42− <O-2< H2O <NCS− < NH3 < en <NO2-1
< CN− < CO (Spectrochemical series---- arrangement of ligands in the increasing order
of their strength to split the d orbital)
(ii) Oxidation state of the central metal ion. A higher oxidation state leads to larger splitting.
 (iii) Size of d orbitals (i.e., transition series): Bigger the size of d orbitals, more the repulsion between
the electrons of ligands and metal ion. Hence larger CFSE.
(iv) Geometry of the complex.
 Splitting of d orbitals of CMI/CMA in octahedral complexes (C N=6): Following figure shows the
arrangement of six ligands (red spheres) around the CMI. The ligands approach the central metal ion along
XX, YY, ZZ axes. (i .e . along d z & d x − y orbitals). Due to this electrons in these orbitals experience more
2 2 2

repulsion than those in dxy, dyz & dzx. This results in splitting of d orbitals as shown below. d z , d x − y orbitals
2 2 2

are called `eg ` orbitals & dxy, dyz ,dzx orbitals are called `t2g` orbitals

∆o = CFSE in octahedral crystal field = (-0.4 x no of electrons in t 2g orbitals + 0.6 x no of electrons in eg orbitals)
 Electronic configuration of d orbital of metal in OCTAHEDRAL complexes:
Since after splitting, the two sets of d orbitals have different energies, electronic configuration of d orbital of
the central metal atom /ion changes in the complex.
 If the ligands are strong filed ligands, then CFSE is very large compared to energy needed to pair the
electrons in an orbital. Then lower energy d orbitals are filled completely before filling the electrons
in the higher energy orbitals {Note that here we are following the normal rules of writing the
electronic configurations}
 If the ligands are weak field ligands, then CFSE < PE (Pairing Energy of electrons) . Then both the sets
of d orbitals are filled with one electron each, before pairing up of electrons starts.
{Note that here we are not following the normal rules of writing the electronic configurations}

 Splitting of d orbitals of CMI/CMA in tetrahedral complexes (C N=4): Following figure shows the
arrangement of four ligands (red spheres) around the CMI. The ligands approach the central metal ion along
XY, XZ, YZ planes. Therefore electrons in dxy, dyz & dzx orbitals experience greater repulsion than the d z & 2

d x − y orbitals. This results in the splitting of d orbital of metal as follows:

2 2
 ∆t = CFSE = (-0.6 x No of electrons in `e` orbitals + 0.4 x No of electrons in `t 2` orbitals)

 Electronic configuration of d orbital of metal in TETRAHEDRAL complexes:

In the case of tetrahedral complexes, CFSE < PE always. Hence while writing the electronic
configurations of CMA/CMI, both the sets of d orbitals are filled with one electron each, before
Pairing up of electrons starts.

 Comparison of splitting of d orbitals of same metal ion in octahedral and tetrahedral field

∆ t = (4/9) ∆o

 Magnetic Properties of the complex: Paramagnetic if unpaired electrons are present in any of the two sets
of d orbitals. Diamagnetic if number of unpaired electrons =0
 Colour of the complex: One of the specialities of majority of complex compounds is that they are coloured
not only in aqueous solution, but also in solid state.

 The unique colour of the complexes can be explained as follows: The energy gap (CFSE), between
two sets of d orbitals of metal in the complexes, lies in the VIBGYOR region. Therefore, when the
white light falls on these complexes, electrons in the lower set of d orbitals can absorb energy
from the visible region of the
spectrum and jump to the higher energy d orbitals. This is known as d-d transition. The transmitted light
which is mixture of other frequencies gives unique colour to the complex

(i) (ii)

Note: * If the metal ion or atom has d0 and d10 configurations then the complex is not coloured as d-d
 transition of electrons does not take place.
* MnO4-1, CrO4-2, Cr2O7-2 ions are coloured even though 3d orbitals of their ions have zero
electrons. This is because electrons from oxygen atoms jump to empty 3d orbitals of these ions
by absorbing energy in the VIBGYOR region.
* Greater the difference between two sets of d orbitals shorter the wavelength (Higher frequency) of the
visible light absorbed by the electron for d-d transition.