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CO-ORDINATION CHEMISTRY
CHEMISTRY P. JOY
CO-ORDINATION CHEMISTRY
MEMORY MAP
Structural Stereooisomerism
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DEFINITIONS
(1) Simple Salts : When an acid reacts with an alkali, neutralisation takes place and a simple salt is
produced,
NaOH + HCl → NaCl + H2O
When dissolved in water, these salts ionise and produce ions in solution. Mixed salts contain more than
one acidic or basic radicals, e.g. NaKSO4.
(2) Molecular or Addition Compounds : When solutions containing two or more salts in stoichiometric
(i.e., simple molecular) proportions are allowed to evaporate, we get crystals of compounds known as
molecular or addition compounds. These are of two types depending on their behaviour in aueous
solution.
(i) Double salts or Lattice Compounds : The addition compounds having the following characteris-
tics are called double salts or lattice compounds
(a) They exist as such in crystalline state.
(b) When dissolved in water, these dissociate into ions in the same way in which the individual
components of the double salts do.
FeSO4.(NH4)2SO4.6H2O → Fe2+(aq) + 2NH4+(aq) + 2SO42(aq) + 6H2O
Mohr's salt
K2SO4.Al2(SO4)3.24H2O → 2K+(aq) + 2Al3+(aq) + 4SO42(aq) + 24H2O
Potash alum
In aqueous solution they give the test of all their constituent ions i.e. the individual components of
a double salt do not lose their identity.
(ii) Coordination (or complex) compounds : It has been observed that when solutions of Fe(CN)2
and KCN are mixed together and evaporated, potassium ferrocyanide, Fe(CN)24KCN is obtained which in
aqueous solution does not give test for the Fe2+ and CN ions, but gives the test for K+ ion and
ferrocyanide ion, Fe(CN)64. The ions [Fe(CN)6]4 is called complex ion & K+ is called counter ion.
Fe(CN)2 + 4KCN → Fe(CN)2.4KCN l 4K+ + Fe(CN)64
Thus we see that in the molecular compound like Fe(CN)2. 4KCN, the individual compounds lose
their identity. Such molecular compounds are called coordination (or complex) compounds.
Complex ion : It may be defined as an electrically charged radical which consist of a central metal
atom or ion surrounded by a group of ions or neutral molecules or both.
A coordination compound consist of either
(i) A simple cation and a complex anion such as K4[Fe(CN)6], or
(ii) A complex cation and a simple anion such as [Cu(NH3)4]SO4
(iii) A complex cation and a complex anion such as [Co(NH3)6][Cr(C2O4)3] or
(iv) A neutral molecule such as Cu(Gly)2, Ni(CO)4 etc.
Coordination sphere : The central metal ion and the ligands that are directly attached to it are
enclosed in a square bracket which Werner has called coordination sphere or first sphere of attrac-
tion. The anions being outside the square bracket form the second sphere of attraction.
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WERNER'S THEORY
Werner's coordination theory which could explain all the observed properties of complex compounds.
More important postulates of this theory are :
(i) Most elements exhibit two types of valencies : Primary valency and (b) Secondary valency.
(a) Primary Valency : This corresponds to oxidation state of the metal ion. This is also called princi-
pal, ionisable or ionic valency. It is satisfied by negative ions and its attachment with the central metal
ion is shown by dotted lines.
(b) Secondary or auxiliary valency : It is also termed as coordination number (usually abbreviated
as CN) of the central metal ion. It is non-ionic or non-ionisable (i.e. coordinate covalent bond type). This
is satisfied by either negative ions or neutral molecules.
(2) Every element tends to satisfy both its primary and secondary valencies. In order to meet this require-
ment a negative ion may often show a dual behaviour, i.e. it may satisfy both primary and secondary
valencies since in every case the fulfilment of coordination number of the central metal ion appears
essential.
(3) The ions attached to primary valencies possess ionizing nature whereas, the ions attached to secondary
valencies do not ionise when the complex is dissolved in a solvent.
(4) Every central ion tends to satisfy its primary as well as secondary valencies.
(5) The secondary valencies are directional and are directed in space about the central metal ion. The
primary valencies are non-directional. The presence of secondary valencies gives rise to stereo-isomer-
ism in complexes.
(6) The geometry of the complex ion depends on the coordination number.
(7) Initially, Werner had pointed out co-ordination number of a metal atom to be four or six.
(8) The six valencies were regarded to be directed to the corners of a regular octahedron circumscribed
about the metal ion. For metals having four co-ordination number, the four valencies are either arranged
in a square planar or tetrahedral nature.
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Sidgwick's concept of Effective Atomic Number - EAN concept (also called Noble Gas Rule) :
Sidgwick suggested that after the ligands have donated a certain number of electrons to the central
metal ion through bonding, the total number of electrons on the central atom, including those gained
from ligands in the bonding is called the effective atomic number (EAN) of the central metal ion and in
many cases this total number of electrons (i.e. EAN) surrounding the coordinated metal ion is equal to
the atomic number of the inert gas.
Example :
EAN of Co(III) in [Co(NH3)6]3+ can be calculated as follows :
Electrons in Coº atom = atomic number of Co = 27 electrons
Electrons in Co3+ ion = 27 3 = 24 electrons
Electrons donated by 6 (: NH3) = 2 × 6 = 12 electrons
EAN of Co(III) in [Co(NH3)6] 3+
= 24 + 12 = 36
EAN (= 36) of Co(III) is evidently equal to the atomic number of Kr.
LIGANDS
The neutral molecules or ions which are directly linked with central metal ion or atom in a complex ion are
called Ligands.
e.g. in the complex ion, [Fe(CN)6]3 the six CN ions are the ligands.
The ligands are attached to the central metal ion or atom through coordinate bond or dative linkage.
CLASSIFICATION OF LIGANDS :
It is classified on the basis of (a) number of donor atoms present in the ligands
(b) charge of ligands
CLASSIFICATION BASED ON THE NUMBER OF DONOR ATOMS PRESENT IN THE LIGANDS
The ligands of this class may be of the following types :
(i) Monodentate or unidentate ligands : The ligands which have only one donor atom and hence can
coordinate to the central metal ion at one site only are called monodentate or unidentate ligands.
(ii) Bidentate, tridentate....... polydentate ligands : The ligands having two, three, four, five or six
donor atoms are called, bi, tri(or ter-), tetra- (or quadri-), penta-, and hexa- dentate ligands
respectively. The bidentate, tridentate. etc. are called polydentate or multidentate ligands (literally
dentate means toothed).
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Table : Some Common Polydentate Ligands.
(Donor atoms having the lone pairs are indicated by asterisks)
2
O
Carbonato OCO
` ` CO 3 2
* *
LM O *
O
OP *
−
MMH C C| = C ||C CH PP
Bi-dentate Acetylacetonato MM 3
| PP 3
(acac)
N H
Q
2 : 2'-Dipyridyl or dipy
2, 2'-dipyridine
N N
* *
LM O O OP 2−
Dimethyl glyoximato
MM *N N* PP (dmg) or (DMG)
MN |
O −
|
OH PQ
* *
Ethylene diamine H2N CH2CH2 NH2 en
Propylene diamine or 1 2 3 pn
CH2 CH CH3
1, 2-diamino propane | |
NH2 NH2
* *
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* *
Isobutylene diamine H2N C(CH3)2 NH2 i-bn
* *
butylene diamine H2N CH(CH3)CH(CH3) NH2 bn
* *
Tetra methyl-ethylene H2N C(CH3)2C(CH3)2 NH2 tetrameen
diamine
8-hydroxyquinolinato (oxin) or
N (oxinate)
O
*
1, 10 phenanthroline o-phen
or o-phenathroline
*
As(CH3)2
o-phenylene bis diars or D
dimethyl arsine
As(CH3)2
*
LM O OP −
Glycinato MMH N CH ||
CO PP (gly)
N* Q
2 2
*
LM NH N
*− OP −
Biguanido
MMNH
* || ||
C NH C NH P
P (Big)
MN 2
PQ 2
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LMOOC
− − OP 2−
Tridentate Imino-di-acetato
MN* H C *NH CH
2 2 COO
* PQ (IDA)2
* *
N N
*
N
2, 2', 2"-terpyridine terpy
H H
Tetradentate Triethylene tetramine H2N (CH2 )2 N (CH2 )2 N trien
* * *
(CH2 )2 NH2
*
- 3-
CH2.COO
*
-
*N CH2.COO
Nitrilo triacetato * (NTA)3
-
CH2.COO
*
-* 3-
OOCCH2
*
-*
OOCCH2
Pentadentate Ethylene diamine
*-
CH2COO
*
triacetato
N
H
- 4-
OOCH2C
* *
-
Hexadentate Ethylene diamine OOCH2C (EDTA)4 Y4
* -
CH2COO
tetraacetato * *
N
-
CH2COO
*
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(c) Positive ligands :
Examples of positively charged monodentate ligands are
NO+ nitrosylium
NH2NH3+ hydrazium
Quite obviously the names of these ligands have the suffix-ium.
(4) Coordination Number (C.N.) or Ligancy : It is the total number of the atoms of the ligands that can
coordinate to the central metal ion. Numerically coordination number represents the total number of the
chemical bonds formed between the central metal ion and the donor atoms of the ligands.
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(1) Naming of Ligands : If the coordination sphere of a given complex compound contains various types of
ligands. The ligands are named in alphabetical order. The prefixes di, tri etc. are not to be considered
while determining this alphabetical order. For example [Co(NH 3) 4 (NO 2)Cl] + ion is named as
tetramminechloronitro cobalt (III) ion.
(2) Naming of the Negative Ligands : In general, if the anion name ends in -ide, -ite or -ate, the final -e
is replaced by o, giving -ido, -ito and -ato respectively, e.g. SO32 (sulphito), SO42 (sulphato), CH3COO
(acetato), S2 (thio or sulphido), NO3 (nitrato), NH2 (imido), NH2 (amino or amine), N3 (azido), NHOH
(hydroxylamido), HON = C(CH3)C(CH3) = NO (dimethylglyoximato).
Some exceptions to this rule are : F (fluoro), Cl (chloro), CN (cyano), O2 (oxo), OH (hydroxo), O22
(peroxo), O2H (perhydroxo).
(3) Naming of the Neutral Ligands : For neutral ligands, the names are not systematic. For less common
neutral ligands (e.g. PH3), the names of free molecules is used as such. For some of the more common
neutral ligands, special names are used e.g., H 2O (aquo), NH3(ammine), CO(carbonyl), NO(nitrosyl),
CS(thiocarbonyl), NS(thionitrosyl).
(4) Naming of the Positive Ligands : Positively charged ligands have suffix ium, e.g. NH 2 NH3+ is called
hydrazinium, and NO+ is nitrosylium.
(6) Naming of the bridging ligands of the bridged polynuclear complexes : The complexes having two
or more metal atoms are called polynuclear complexes. In these complexes the bridging group is indi-
cated in the ormula of the complex by separating it from the rest of the complex by hyphens and by
adding the prefix µ before its name. The Greek letter µ should be repeated before the name of each
different bridging group.
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Examples :
OH
(N H 3 ) 5 C r µ-hydroxo-bis {penta-ammine chromium (III)} chloride
(N H 3 ) 5
C l5
NH2 4+
(N H 3 ) 4 C o
C o(N H 3 ) 4 µ-amido-µ-nitro octa-ammine dicobalt (III) ion
NO2
(2) Cationic and neutral complexes : In case of cationic and neutral complexes like [Cr(H2O)4Cl2]+,
[Cu(NH3)4]2+, [Ni(CO)4], central metal ion followed by a Roman numeral in parentheses to indicate its
oxidation state. The suffix ate is not attached to the name of the metal in case of these complexes.
Examples :
[CrIII (H2O)4 Cl2]+ Dichloro-tetra-aquo chromium (III) ion Cationic complexes
[Al (OH) (H2O)5]
III 3+
Hodroxo pentaaquo aluminium (III) ion Cationic complexes
[Ni0(CO)4]0 Tetra carbonyl Nickel (0) Neutral
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1. STRUCTURAL ISOMERISM :
(i) Ionization isomerism
(a) Complexes having same empirical formula but producing different ions in solution state, e.g.
[Co(NH3)5Br] SO4 and [Co(NH3)5SO4]Br
Pentaamminebromocobalt (III) sulphate Pentaamminesulphatocobalt (III) bromide
(Violet) (Red)
(b) Scuh an isomerism is due to the interchange of groups between the co-ordination sphere of
the metal ion and the ions outside the sphere.
(ii) Hydration isomerism : This isomerism arises when different number of water molecules are
present within and outside the co-ordination sphere. For example, 3 hydration isomers of CrCl3.6H2O
are ;
[Cr(H2O)6]Cl3 [Cr(H2O)5Cl]Cl2.H2O [Cr(H2O)4Cl2]Cl.2H2O
Violet Green Green
(iii) Linkage isomerism : This isomerism arises when ligand has two possibilities in its mode of attach-
ment to the metal atom. For example, the ligand NO2 binds with metal atom through N or O in the
following example.
[Co(NH3)5ONO]Cl2 [Co(NH3)5NO2]Cl2
Pentaamminenitritocobalt(III) chloride Pentaamminenitrocobalt(III) chloride
(Red) (Yellow)
(iv) Ligand Isomerism : As the name imlies, ligands isomerism arises from the presence of ligands
which can adopt different isomeric forms An example is pronded by diaminopropane which have the
amine groups in the terminal or adjacent position.
e.g., [Co(pn)2Cl2]+, [Co(tn)2 Cl2]+, [Co(pn)(tn)Cl2]+
(iv) Co-ordination isomerism : This isomerism exist in polynuclear complex (where both complex
anions and complex cations are present) by partial or complete exchange of ligands. For example,
[Cr(NH3)6].[Cr(SCN)6] and [Cr(NH3)4(SCN)2].[Cr(NH3)2.(SCN)4]
[Co(NH3)6].[Cr(C2O4)3] and [Cr(NH3)6].[Co(C2O4)3]
[Co(en)3].[Cr(CN)6] and [Cr(en)3].[Co(CN)6]
(v) Co-ordination position Isomerism : This type of isomerism is exhibited by polynuclear complexes
by changing the position of ligands with respect to different metal atoms present in the complex
e.g.,
OH OH
(NH3)4 Co Co (NH3)2Cl2 SO4 Cl(NH3)3 Co Co (NH3)3Cl SO4
OH OH
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(vi) Polymerisation Isomerism : This isomerism arises when compounds have the same stoichiomet-
ric composition but different molecular composition (which is an integer multiple of stoichiometric
composition),
Square planar complexes having formula M A2B2 , MA 2BC , M ABCD show geometrical isomerism
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EXAMPLES :
(i) [Pt(NH3)2Cl2] resembling to formula MA 2B2 exists in cis and trans forms
(iii) Complexes of MABCD type exist in 3-geometrical isomeric forms e.g., [Pt(NH3) (NH2OH) (py) (NO2)]+
(iv) Complexes of M A2 type may also show geometrical isomerism in square planar complexes where A is
unsymmetrical bidentate ligand. e.g., [Pt(NH2CH2COO)2]
(v) Bridged complex of type M2 A2B 4 also exists as cis and trans-isomers.
e.g., [Pt.Cl2.P(C2H5)3]2
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MEMORY CHART : GEMETRICAL ISOMERISM IN SQUARE PLANAR COMPLEXES
Symmetrical Unsymmetrical
MA" MA BC MABCD bidentate ligand
bidentate ligand
(Will not show G.I.) (Will (Will
show G.I.) show G.I.) M(AA) M(AA)
(Will not (Will
show G.I.) show G.I.)
MA!B MA B MAB!
(Will not (Will (Will not
show G.I.) show G.I.) show G.I.)
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e.g., [RhCl3(py)3]
(iii) Complexes of type M(A)3 also show geometrical isomerism where A is bidentate unsymmetrical
ligand. e.g., [Cr(NH2CH2COO)3]
(iv) Complexes of type M(A)2 B2 or M(A)2 BC also show geometrical isomerism, here A is symmetrical
bidentate ligand.
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S.No. Complex having Co-ordination No. 6 Number of Geometrical isomers
1. MA6 0
2. MA5B 0
3. MA4B2 2
4. MA3B3 2
5. MA 2B2C2 5
6. MABCDEF 15
OPTICAL ISOMERISM :
(a) A coordination compound which can rotate the plane of polarised light is said to be optically
active.
(b) When the coordination compounds have same formula but differ in their abilities to rotate direc-
tions of the plane of polarised light are said to exhibit optical isomerism and the molecules are
optical isomers.
(c) The optical isomers are pair of molecules which are non-superimposable mirror images of each
other.
(d) The isomer which rotates the plane of polarised light to right direction is termed dextro (d-form)
while the isomer which rotates plane of polarised light to left direction is termed laevo (l-form).
(e) The two optically active isomers are collectively called enantiomers. Enantiomers are mirror imgae
to each other and their physical properties are different.
CH! CH!
H!C CH!
O C C O
C O O C
HC Be CH H C C H
C O O C
O C C O H#C$
H#C$
C$H# H#C$
Mirror plane
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Examples :
(i) [Ma2 b2 c2 ]n±, e.g., [Pt(py)2(NH3)2Cl2]2+
py 2+ py 2+
Cl py py Cl
Pt Pt
Cl NH3 NH3 Cl
NH3 NH3
Cis-d-isomer Mirror Cis-l-isomer
Br Br
py NO2 O2N py
Pt Pt
Cl NH3 H3N Cl
I I
d-isomer Mirror I-isomer
en 3+ en 3+
en
Co Co en Co en en
en
en
en
'Meso' or optically inactive form
d-form Mirror l-form
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(iv) [M(AA)2a2]n±, e.g., [Co(en)2Cl2]+
en + en +
Cl Cl
Co Co
Cl Cl en
en
Cis-d-isomer Mirror Cis-l-isomer
2+ en 2+
en
Cl Cl
Co Co
H3N en NH3
en
Cis-d-isomer Mirror Cis-l-isomer
gly gly
Cr gly Cr
gly
gly gly
Cis or trans-d-isomer Mirror Cis or trans-l-isomer
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Ma6 1 0
Ma5b 1 0
Ma4 b2 2 0
Ma3 b3 2 0
Ma4 bc 2 0
Ma3bcd 5 1
Ma2bcde 15 6
Mabcdef 30 15
Ma 2 b 2 c 2 6 1
Ma2 b2 cd 8 2
Ma3 b 2 c 3 0
M(AA)(BC)de 10 5
M(AB)(AB)cd 11 5
M(AB)(CD)ef 20 10
M(AB)3 4 2
M(ABA)cde 9 3
M(ABC)2 11 5
M(ABBA)cd 7 3
M(ABCBA)d 7 3
M(AA)3 2 1
Capital letters represent chelating ligands, lower case represent monodenatate ligands.
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(i) The central metal atom provides a number of empty orbitals equal to its co-ordination number for the
formation of covalent bonds (or more accurately co-ordinate bonds) with ligand orbitals.
(ii) The empty orbitals of the metal ion hybridize to give an equal no. of hybrid orbitals of equivalent energy.
(iii) The metal atom or ion can use (n 1)d, ns, np, nd orbitals for hybridization to yield square planar,
tetrahedral or octahedral geometry.
(iv) These hybridized orbitals then overlap with ligand orbitals which can donate an electron pair for bonding.
(v) If the complex contains unpaired electrons, the complex is paramagnetic in nature whereas, if it does
not contain unpaired electrons, the complex is diamagnetic in nature.
(vi) Under the influence of a strong ligand (like, NH3, CN, CO, etc.), the electrons can be forced to pair up
against the Hund's rule of maximum multiplicity.
4 sp3 6 d2sp3
4 dsp2 6 sp3d2
Step-6 : Now vacant appropriate number of 'd' orbital to have an empty set of obitals for hybridisation.
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Table : Co-ordination numbers, hybridized orbitals and geometry of some co-ordination com-
pounds
Number
2 sp [Ag(NH3)2]+, [Ag(CN)2]
3 sp2 [HgI3]
orbital.
dz2 orbital.
orbital.
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Table : Geometry (shape) and magnetic nature of some of the complexes (Application of
valence bond theory)
bipyramidal
Limitations of valence bond theory : The valence bond theory was fairly successful in explaining
qualitatively the geometry and magnetic properties of complexs. However, it has a number of
limitations.
(i) The theory does not offer any explanation why most of complexes are coloured
(ii) The theory does not offer any explanation for the existence of inner-orbital and outer-orbital
complexes.
(ii) The theory does not explain why certain complexes are labile while others are inert.
(iii) In the formation of [Cu(NH3)4]2+, one electron is shifted from 3d to 4p-orbital. The theory
is silent about the energy availability for shifting such as electron. Such an electron can be
easily lost, then why [Cu(NH3)4]2+ complex does not show reducing properties.
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CRYSTAL FIELD THEORY (CFT)
(i) CFT regards a complex as a combination of a central ion surrounded by other ions or molecules with
electrical dipoles (i.e., ligands). It considers these ligands as point charges or as point dipoles.
(ii) In its simplest treatment CFT does not consider covalent bonding in complexes, but the bonding be-
tween the metal cation and ligands arises from the electrostatic attraction between the nucleus of the
metal cation and the partial negative charge invariably present on the ligands. The interaction between
the electrons of cation and those of the ligands is entirely repulsive. It is these repulsive forces that are
responsible for causing the splitting of the d-orbitals of the metal cation. The bonds between the metal
and the surrounding ligands are thus purely ionic.
(iii) The CFT does not provide for electrons to enter the metal orbitals. Thus the metal ion and the ligands
do not mix their orbitals or share electrons i.e., it does not consider any orbital overlap.
(iv) CFT gives a representation of bonding that is purely an electrostatic or coulombic interaction between
positively charged (i.e., cation) and negatively charged (i.e., anions or dipole molecules which act as
ligands) species.
(v) Crystal field theory assumes ligands as point charges and the attraction between the central metal and
the ligands in a complex is purely electrostatic. In an isolated gaseous metal ion, the five d orbitals do all
have the same energy (degenerate). But in octahedral & tetrahedral complexes, the energy of the d-
orbitals is raised because of repulsion between the field produced by the ligand and the electrons on the
metal.
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(ii) The electrons in d-orbitals of the metal cation are repelled by negative point charge or by the
negative end of the dipole of the ligands.
(iii) This repulsion increase the energy of all the five d-orbitals.
(iv) If all the ligands approaching the metal cation are at an equal distance from each of d-orbitals (i.e.,
the ligand field is spherically symmetrical), the energy of each of the five d-orbitals increases by
the same amount, i.e., all the d-orbitals remains degenerate, although they possess higher energy.
(v) However, this is not possible as it is only hypothetical situation.
(vi) Since the lobes of two eg orbitals is lie in the path of approaching ligands see, fig. The electrons
in these orbitals experience greater force of repulsion than those in t2g orbitals whose lobes are
directed in space between the path of the ligands see fig. i.e, energy of eg orbitals is increased
while that of t2g orbitals is decreased.
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(vii) Thus, an energy difference exists between two sets of orbitals.
(viii) This energy difference is called crystal field splitting energy and is represented by ∆O (the subscript
O stands for octahedral). It measures the crystal field strength of the ligands.
(ix) The crystal field splitting occurs in such a way that average energy of the d-orbitals does not
change.
2
(x) Thus, three orbitals lie at an energy that is ∆ below the average orbital energy and two d-orbitals
5 0
3
lie at an energy ∆0 above the energy.
5
Fig :
(xi) The energy gap between t2g and eg sets is also denoted by 10 Dq.
(xii) Energy of t2g orbitals is 4Dq less than that of hypothetical degenerate d-orbitals and that of eg
orbitals is 6Dq above that of the hypothetical degenerate d-orbitals. Thus, t 2g set loses an energy
equal to 0.4 ∆0 or Dq while eg set gains energy equal to 0.6 ∆0 or 6 Dq.
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4
∆t = ∆O
9
t2g1, 2, 3
→ eg
4, 5
→ t2g
6, 7, 8
→ eg
9, 10
(iii) In complexes of weak ligands, ∆O is less than P(P is called average pairing energy which is
the energy required to pair two electrons in the same orbital). ∆O, the octahedral crystal field
splitting energy, tends to force as many electrons to t2g set while P tends to prevent the
electrons to pair in the t2g level.
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(b) When the ligands are strong :
(i) Under the influence of strong ligands, the energy difference between t 2g and eg sets is
relatively high and thus the distribution of d-electrons in t2g and eg sets does not obey Hund's
rule.
(ii) The first electrons numbered 1, 2, 3, 4, 5, 6 will go to t 2g set and remaining four electrons
numbered 7, 8, 9 and 10 will go to eg set.
t2g1, 2, 3, 4, 5, 6
→ eg7, 8, 9, 10
Strong field (Low spin complexes) Weak field (High spin complexes)
∆O > P ∆O < P Common
dxions
Config- No. of spin Config- No. of spin examples
uration unpaired uration unpaired
electrons electrons
d1 t 2g 1 eg o 1 1/2 t 2g1 ego 1 1/2 Ti3+
d2 t 2g 2 eg o 2 1 t 2g2 ego 2 1 V3+
d3 t 2g 3 eg o 3 3/2 t 2g3 ego 3 3/2 Cr3+
d4 t 2g 4 eg o 2 1 t 2g3 e g1 4 2 Mn3+
d5 t 2g 5 eg o 1 1/2 t 2g3 e g2 5 5/2 Mn2+,Fe3+
d6 t 2g 6 eg o 0 0 t 2g4 e g2 4 2 Fe2+,Co3+
d7 t 2g6 eg 1 1 1/2 t 2g5 e g2 3 3/2 Co2+
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Weak field (high spin complexes) Strong field (Low spin complexes)
1
d3 t2g1 e g2 3 1 t 2g0 e g3 1 1/2
2
d4 t2g2 e g2 4 2 t 2g0 e g4 0 0
1
d5 t2g2 e g2 5 2 t 2g1 e g4 1 1/2
2
d6 t2g3 e g3 4 2 t 2g2 e g4 2 1
1 1
d7 t2g3 e g4 3 1 t 2g3 e g4 3 1
2 2
d8 t2g4 e g4 2 1 t 2g4 e g4 2 1
d9 t2g5 e g4 1 1/2 t 2g5 e g4 1 1/2
d 10 t2g6 e g4 0 0 t 2g6 e g4 0 0
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SPECTROCHEMICAL SERIES
(i) For any given metal cation, the magnitude of crystal field splitting energy depends on the nature
of ligands.
(ii) The greater the ease with which the ligand can approach the metal ion, the greater wil be the
crystal field splitting caused by it.
(iii) The ligands which affect only a small degree of crystal field splitting are termed weak field ligands.
(iv) When the ligands are arranged in order of the magnitude of crystal field splitting, the arrangement,
thus, obtained is called spectrochemical series.
I > Br < Cl < NO3 < F < OH < OX2 < H2O < py = NH3 < en < dipy < o-Phen < NO2 < CN < CO
Weak field ligands Increasing crystal field Strong field ligands
(v) From the above arrangement it is clear that ligands before H2O such as I, NO3, OH, etc. are
weak field ligands while the ligands after H2O such as NO2, CN, CO etc., are strong field ligands.
(vi) Stronger field ligands cause greater crystal splitting i.e., ∆O value for octahedral compelx is high.
(vii) Besides the nature of ligands, there are some other factors which affects the crystal field splitting
energy. These factors are :
(a) The identity of the metal : The crystal field splitting, ∆, is about 50 percent higher for the
second transition series compared to the first whereas the third series is about 25 percent
higher than second. There is a small increase in the crystal field splitting along each series.
(b) The oxidation state of the metal : Generally, the higher the oxidation state of the metal, the
greater the crystal field splitting. For example, most of the cobalt (II) complexes have low
values of ∆ whereas all cobalt (III) complexes have high values of ∆.
4
(c) The number of ligands : The crystal field splitting for a tetrahedral environment is about
9
that for an octahedral environment.
Application of CFT
Crystal field theory have the following applications
(1) It can provide an explanation for the observed colours of transition metal complexes.
(2) It is helpful in determining the number of unpaired electrons in a high spin (HS) and low spin
(LS) octahedral complexes.
(3) It is used in determining magnetic moment of complexes.
(4) It is used in calculating crystal field stabilisation energy (CFSE).
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(i) A coordination compound is formed in solution by the stepwise addition of ligands to a metal ion.
(ii) Thus, the formation of the complex, MLn (M = central metal cation, L = monodentate ligand and
n = coordination number of metal ion) may be supposed to take place by the following n consecutive
steps.
M + L ML
[ML]
K1 = ML + L ML2
[M][L]
[ML 2 ]
K2 =
[ML][L]
ML2 + L ML3
[ML 3 ]
K3 = [ML ][L]
2
MLn1 + L MLn
[ML n]
Kn = [ML ][L]
n−1
(iii) With a few exceptions, the values of successive stability constants decrease regularly from K1 to
Kn.
M + nL Mn
[ML n ]
K = K1 K2 K3,......Kn =
[M][L]n
(v) The higher the overall stability constant value of the complex, the more stable it is.
(vi) Alternatively 1/k value called instability constant explain the dissociation of the complex into metal
ion and ligands in the solution.
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(vii) The values of stability constants for some of the complex are given below :
(a) The values of stability constants differ widely depending on the nature of the metal ion and
the ligand. In general, higher the charge density on the central ion, the greater is the stability
ch arg e
of its complexes, i.e., the higher value of , the greater is the stability of its
radius of the ion
complexes.
(b) Electronegativity of the central ion influences the stability. The higher the electronegativity
of the central ion, the greater is the stability of its complexes.
(c) The more basic a ligand, the greater is the ease with which it can donate its lone pairs of
electrons and therefore, the greater is the stability of the complexes formed by it.
(d) The higher the oxidtation state of the metal, the more stable is the complex. The charge
density of Co3+ ion is more than Co2+ ion and thus, [Co(NH3)6]3+ is more stable than
[Co(NH3)6]2+. Similarly, [Fe(CN)6]3 is more stable than [Fe(CN)6]4.
(e) The cyano and ammine complexes are far more stable than those formed by halide ions. This
is due to the fact that NH3 and CN are strong Lewis bases.
(f) The complexes of bivalent cations (M2+) of 3d-series show the following order of stability :
decrease
(e) Chelating ligands form more stable complexes as compared to monodentate ligands.
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METAL CARBONYLS
(1) Metal carbonyl show exceptionally high stability than the expected stability by their normal bonding
This can be explained by concept of back bonding.
(2) Metal have 2 types of orbital
(a) Vacant valence orbitals
(b) Some partilly d-orbitals.
(3) In metal carbonyls metals forms a σ bond with ligand where ligand donates its e pair into vacant
orbitals of metals.
(4) The excess e deposited on metal by the ligand is relieved by back bonding where metal donates
back from its filled orbitals into vacant anti-bonding orbitals of CO. This extra back-bonding is called
Synergic back-bonding which imparts extra bond strength and metal carbonyls turns more stable
Vacant *
π molecular orbital on CO molecule
Ni-Co π bond
+ +
Ni :C O: Ni :C O:
+ + +
2 2
Filleed dx -y orbital on Ni Atom
ORGANOMETALS
Organometal compounds are divided into two class :
(1) These are sigma complexes (σ-organometals)
(2) π-complexes.
In σ complexes metal and ligands are bonded by direct σ-bond whereas π- complexes has
ligands with molecular π-electron which are donated into metal vacant orbital.
In π complexes ligands molecular donate π-electrons of their molecular orbital which are denoted
by η2, η3, η4 ..... etc depending on number of atom which constitute the π molecular orbital.
Note :
(a) Ferrocene and dibenzne chromium are examples of sandwitch compounds where the ligands ring
covers the metal ion from both top & bottom.
(b) Zieses salt is used as antitumour drug in which ethene ligand act as π-ligand.
(c) K4[Fe(CN)6] is not called an organometal although there is direct sigma bond between metal
and carbon.
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Examples of σ-Complexes π-Complexes
(i) CH3MgX (i) Ziesel salt K[Pt(η2CH2=CH2)]
(ii) R2Zn (ii) Dibenzene cromium [Cr (C6H6)2]
(iii) Et4Pt (TEL) (ii) Ferrocene [Fe(η5 C5H5)2]
(iv) R2CuLi
(v) R4Sn
π -Complexes
(i) Homogeneous catalysis : A large number of reactions in solutions are catalysed by organometallic
compounds or intermediates derived from transition metal complexes. For example, Wilkinson's
catalyst, (Ph3P)3RhCl.
(ii) Heterogeneous catalysis : Organometallic compounds can also be used as heterogeneous cata-
lysts, e.g., trialkyl aluminium.
(iii) Organic synthesis : They ar widely used in synthesis of various types of organic compounds. e.g.,
organolithium and organomagnesium compounds are commonly used for the synthesis of different
types of organic compounds.
(iv) Medicine : A number of organo arsenic compounds are used as main remedy for syphilis.
(v) Agriculture : To prevent the infection of young plants, the seeds are treated with organometallics
such as ethyl mercury chloride.
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The complexes are of immense importance on account of their applications in various fields. During
complex formation there are drastic changes in the properties of metal atom or ion and these changes
in properties are made use of in the applications of metal complexes.
1. Analytical chemistry : Coordination compounds find their applications in both separation and
detection of cation and anion.
(A) Separation :
(i) The separation of Ag+ from Hg22+ in the first group of analysis is based on the fact that white
silver chloride is soluble in aqueous ammonia and Hg2Cl2 forms a black insoluble material.
Soluble
(ii) The separation of II B group sulphides from IIA group sulphides is based on the fact that
sulphides of IIB group form complex sulphides with yellow ammonium sulphide which are soluble
while sulphides of IIA group do not react.
(B) Detection : Detection of cation / anion is based on the formation of coloured complexes.
be detected
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S.No. Cation / Anion to Complex formed Colour of complex
be detected
O
OH
| A
N = C − CH3
CH3 − C = N
| Ni |
9. Ni2+ CH3 − C = N N = C − CH3 Scarlet red complex
B |
OH
O
(acetate)
(Ring Test)
(C) Many ligands (organic reagents) are used for the gravimetric estimation of a number of metal ions.
Fe 3+ 1,10-phenanthroline
Al3+ 8-hydroxyquinoline
(D) EDTA is used as a complexing agent in volumetric analysis of metal ions like Ca2+, Mg2+ and Zn2+.
(E) The coordination compounds of the transition metals exhibit a variety of colours. The property
is utilised in colorimetric analysis for the estimation of many metals.
The complex 'Ferroin' [FeII(Phen)3]2+ (Bright red colour) is a useful redox indicator.
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2. Metallurgical operations : Silver and gold are extracted by the use of complex formation. Silver
ore is treated with sodium cyanide solution with continuous passing of air through solution. Silver
dissolves as a cyanide complex and pure silver is precipitated by the addition of scrap zinc.
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The water ligand can be replaced eadily by molecular oxygen to form red coloured oxy-
haemoglobin.
Structure of oxy-haemoglobin
(ii) Chlorophyll : The chlorophyll molecule, which plays an essential role in photosynthesis also
contains the porphyrin ring but the metal ion there is Mg2+ rather than Fe2+.
(iii) Vitamin B12 : It is a complex of cobalt with a quadridentate ligand which is similar to porphyrin
ligand of haemoglobin.
6. Plant growth : Iron in +3 state present in the soil is mostly hydrolysed to form insoluble iron hydroxide
Fe(OH)3, which cannot be taken up by plants. To overcome iron deficiency, the complex Fe(III)-EDTA
is added to the soil. This complex is soluble in water and readily enters the roots of trees and reach
to various parts of the plants where it is converted into useful compounds.
7. In medicinal field :
(i) The complex of calcium with EDTA is used for the treatment of lead poisoning. Lead readily replaces
calcium in the complex and lead-EDTA complex is finally eliminated from the body in urine.
(ii) The platinum complex cis [Pt(NH3)2Cl2] known as cis-platin is used as an antitumor agent in the
treatment of cancer.
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