Co Ordination Compounds PDF

CHEMISTRY BY: T.K.
ARORA: CBSE, ICSE, PMT, IIT- JEE, AIEEE, IB, SAT-II: 98111-45-20
CO-ORDINATION COMPOUNDS
Chemistry Notes Series
Code: CC/NT
Time:
M.M.
Class –XII.
Unit 9
Coordination Compounds
 Werner’s Postulates :
The mains postulates are:
 In coordination compound metals shown two types of linkages (valences) primary and sec-
ondary.
 The primary valences are normally ionisable and are satisfied by negative ions.
 The secondary valences are non-ionisable. These are satisfied by neutral molecules or
negative ions. The secondary valance is equal to the coordination number and is fixed for a
metal.
 The ions/ groups bonds by the secondary linkages to the metals have characteristic spatial
arrangements corresponding to different coordination number.
 Difference between a double salt and a complex :
Both double salts as well as complexes are formed by the combination of two or more stable
compounds in stoichiometric ratio. However, they differ in the fact that double salts as car-
nalallite, KCl. MgCl2. 6H2O dissociate into simple ions completely dissolved in water.
However complex ions as [Fe(CN)6]4- or K4Fe(CN)6 do not dissociate into Fe2+ and CN-
ions.
 Definitions of Some Important Terms Pertaining to Coordination compounds
 Coordination entity
 It constitutes a central metal atom or ion bonded to a fixed number of ions or mole-
cules.
 [The whole thing written in square bracket]

 [COCl3(NH3)3] is a coordination entity in which the cobalt ion is surrounded by three
ammonia molecules and three chloride ions.
 (Ni(CON)4] , [PtCl2 (NH3)2] [Fe(CN)6]4- [CO(NH3)6]3+
Central atoms/ion
 In coordination entity. The atom/ ion to which a fixed number of ions /groups
are bond in a definite geometrical arrangement around it is called the central
atoms or ion.
 The central atoms ion in the coordination entities; [NiCl2 (H2O)4] [CoCl(NH3)5]2+
and [Fe(CN)6]3- are Ni2+ ,CO3+ and Fe3+ respectively.
 Central atoms/ ions are Lewis Acids.
Ligands
 The ions and molecules bound to the central atoms/ ion in the coordination en-
tity are called ligands.
 These may be simple ions such as Cl- small molecules such as NH3 and H2O.
 Large molecules such as H2NCH2CH2NH2 or N(CH2CH2CH3)3 or even macro-
molecules. Such as proteins.
CHEMISTRY BY: T.K. ARORA: CBSE, ICSE, PMT, IIT- JEE, AIEEE, IB, SAT-II: 98111-45-20 1
CHEMISTRY BY: T.K. ARORA: CBSE, ICSE, PMT, IIT- JEE, AIEEE, IB, SAT-II: 98111-45-20
 Denticity :
 The number of bonds a ligand makes with any central metal atom or ion.
 Unidentate / Monodentate:
 When a ligand is bonded to a metal ion through a single donor atoms.
 Cl- , H2O or NH3 .
 Didentate:
 When a ligand can bind through two donor atoms.
 H2NCH2CH2NH2 (ethane -1,2 diamine) or C2O4-2 (oxalate).
 Didentate:
 Several donor atoms are present in a single ligand. The ligand is said to be
polydentate.
 Ethylendiamineteraacetate ion (EDTA4-) is an important hexadentate ligand.
 It binds through two nitrogen and four oxygen atoms to a central metal ion.
.. CH3COO-
H2C N
CH3COO- M
CH3COO-
H2C N
..
CH3COO-
 Ambidentate:
 Ligand which can ligate through two different atoms / ion.
 Nitro i.e. NO2 (can bind through N and O ), Cyno CN- (can bind through C and
N ), and isocynide SCN- (can bind through S and N )
 CHELATION AND CHELATE LIGAND :
 When a di or polydentate ligand uses its two or more donor atoms to bind a
single metal ion, it is said to be a chelate ligand, and the phenomenon is CHE-
LATON.
 Chelated complexes tend to be more stable.
 MORE THE CHELATION MORE STABLE THE COORDINATION COM-
POUND IS.
O
M N M O N O
O
Nitrito –N Nitrito –O
M  SCN M  NCS
Thiocyanate Isothiocyanato
Coordination number
 The coordination number (C.N.) of a metal ion in a complex can be defined
as the number of ligand donor atoms to which the metal is directly bonded.
 For example. In the complex ions, [PtCl6]2- and [Ni(NH3)4]2- the coordinate
number of Pt and Ni are 6 and 4 respectively.
 In the complex ions, [Fe(C2O4)3]3- and [Co(en)3]3+ the Coordination num-
ber of both Fe and Co, is 6 because C2O42- and en (ethane -1,2 – diamine)
are dentate ligands.
 coordination number of the central atoms/ ions is determined only by the
number of sigma bonds formed by the ligand with the central atoms / ion.
 Pi bond, if formed between the ligands and the central atom/ ion are not
counted for this purpose.
Coordination sphere
 The central atom ion and ligands attached to it are enclosed is square
bracket and is collectively termed as the coordination sphere.
 For examples in the complex K4[Fe(CN)6] the coordination sphere is
[Fe(CN)6]4- is octahedral.
 [Ni(CO)4] is tetrahedral and [PtCl4]2- is square planer.
Counter Ion :
 The ionisable groups which are written outside the bracket and are called
counter ions.
Oxidation number of central atom
 The oxidation number of the central atom in a complex is defined as the
charge it would carry, if all the ligands are removed along with the electron
pairs that are shared with the central atom.
 The oxidation number is represented by a roman numeral in parenthesis fol-
lowing the name of the coordination entity.
 Oxidation number of copper in [Cu(CN)4]3- is +1 and it is written as Cu(I).
Homolepetic and heteroleptic complexes
 Complexes in which a metal is bound to only one kind of donor groups. e.g.,
[Co(NH3)6]3+ are known as homoleptic.
 Complexes in which a metal is bund to more than one kind of donor groups.
E.g. [CO(NH3)4 Cl2]+ are known as heteroleptic.
 Nomenclature of Coordination Compounds
 Formulas from the IUPAC names:
 The central atom is listed first.
 The ligands are then listed in alphabetical order. The placement of a ligand in the list
does not depend on its charge.
 Polydentate ligands are also listed alphabetically. In case of abbreviate ligand the first
letter of the abbreviation is used to determine the position of the ligand in the alpha-
betical order.
 The formula for the entire coordination entity whether charged or not is enclosed in
square brackets. When ligands are polyatomic, their formulas are enclosed in paren-
theses. Ligand abbreviations are also enclosed in parentheses.
 There should be no space between the ligands and the metal within a coordination
sphere.
 When the formula of a charged coordination entity is to be written without that of the
counted ion the charge is indicated outside the square brackets as a right superscript
with the number before the sign. For examples [Co(CN) 6]3- [Cr(CH2O)6]3+ etc.
 The charge of the cation (s) balanced by the charge of the anion (s).
 Naming of (IUPAC) Coordination Compounds

 The cation is named first in both positively and negatively charged coordination enti-
ties.
 The ligands are named in an alphabetical order before the names of the central atom /
ion.
 Names of the anionic ligands end with – O .
 Names of neutral and cationic ligands are the same except aqua for H 2O, ammine for
NH3. Carbonyl for CO and nitrosyl for NO.
 Prefixes mono, id tri catch., are used to indicate the number of the individual ligands
in the coordination entity,
 When the names of the COMPLEX ligands include a numerical prefix then terms,
bis, Tris, tetracis are used.
 Oxidation state of the metal in cation, anion or neutral coordination entity is indicated
by Roman numeral in parenthesis.
 If the complex ion is an anion, the name of the metal ends with the suffix ate. For
example Co in complex anion, [Co(SCN)4]2- is called cobaltate.
 For some metals, the Latin names are used in the complex anions, e.g., Ferrate for Fe.
 The neutral complex molecular is named similar to that of the complex cation.
 [Cr(NH3)3 (H2O)3] Cl3 is named as:
Triamminetriaquachromium (III) chloride
O.N. of Cr: x + 0+ 0 -3 = 0; x = +3
 [Co(H2NCH2CH2NH2)3]2 (SO4)3 is named as:
Tris (ethane -1,2- diamine) cobalt (III) sulphate
O.N. of Co: 2x + 0 -3(2) = 0; x = +3
 [Ag(NH3)2] [Ag(CN)2] is named as:

Diamminesilver (I) dicyanoargentate (I)
 Isomerism:
 (A) Structural isomerism (B) stereo isomerism or space isomerism.
(A) Structural Isomerism :
 Ionisation isomerism:
 Compounds which give different ions in solution although they have same molecular formula.
 This type of isomerism occurs when counter ion of the complex is also a potential ligand.
 [Co(NH3)5 Br]2+ SO42- i.e., Pentaamminebromidocobalt(III) sulphate is red violet and in solu-
tion gives a precipitate with BaCl2 Confirming the presence of SO42- ion.
 While [Co(NH3)5 (SO4)]+ Br-, i.e., Pentaamminesulphatocobalt (III) bromide is red and does
not give test for sulphate ion in the solution, but instead gives a precipitate of AgBr with
AgNO3. Other examples of ionization isomerism are:
 [Pt (NH3)4 (OH)2]( SO4) and [Pt (NH3)4 (SO4)] (OH)2
 [Pt(NH3)4 Cl2] Br2 and [Pt(NH3)4 Br2 ]Cl2

 [Co (NH3)5NO3] SO4 and [Co(NH3)5 (SO4)] NO3
 Solvate or Hydrate isomerism:
 Compound which have the same composition but differ in the number of solvent molecules
present as ligands (i.e., in the coordination sphere) and as free solvent molecules (present out-
side the coordinate sphere) in the crystal lattice are called solvate isomers.
 If water is the solvent these are called hydrate isomers.
 Three different hexa hydrates of chromic chloride with an empirical formula of CrCl 3.6H2O.
 All the three differ in the number of molecules of water in the coordination sphere.
 The formula which have been assigned to these hydrate isomers are:
[Cr(H2O)6]Cl3 [Cr(H2O)5 Cl] Cl2H2O [Cr (H2O)4 Cl2] Cl. 2H2O
Violet Blue green Dark green
(There ionic chlorines (Two ionic chlorines) (One ionic chlorine)
 [Co (NH3)4 (H2O)] Cl2 and [Co(NH3)4 Cl2] Cl. H2O
 [CoCl(NH3)4 (H2O)] Br2 and [CO(NH3)4 Br2] Br. H2O. These are also ionization isomers.
 Linkage isomerism:
 Isomerism of this type occurs in compounds containing ambidentat ligands.
 When more than one atom in a unidentate ligand may function as a donor.
 In the case of the ligand NO2-, either nitrogen or an oxygen atom my act as a donor, giving
two different isomers.
 Pentaamminenitritocobalt (III) chlorides have been prepared each containing one NO2 groups
in the complex ion.
 One is red and is easily decomposed by acids to give nitrous acid while the other is yellow and
is stable to acids.
 This behaviour is analogous to the behaviour of organic nitrites RONO (easily decomposed by
acids to give nitrous acid ) and nitro compounds RNO2(stable to acids).
NH3 2+ NH3 2+
H3N ONO H3N NO2
CO CO
H3N NH3 NH3 NH3
NH3 NH3
Pentaamminenitrito-O-cobalt (III) Pentaamminenitrito-N-cobalt (III)

Ion (Red) Ion (yellow)
Some other examples are

 [Cr(H2O)5 (SCN)]2+ and [Cr(H2O)5 (NCS)]2+
 [CO(NH3)2 (NO2)2 (py)2] NO3 and [CO(NH3)2 (ONO)2 (py)2] NO3
 Coordination isomerism:
 This type of isomerism is possible when either positive and negative ions or a salt are
complex ions and the two isomers differ in the distribution of ligands in the cation (posi-
tive ion) and the anion (negative ion). Some important examples are:
 [Co (NH3)6 [Cr(CN)6] and [Cr(NH3)6 ] Co(CN)6]
 [Cr (NH3)6] [Co(C2O4)3 and [Co (NH3)6] [Cr(C2O4)3]
 [Co (en)3] Cr (CN)6] and [Cr(en)3] [Co(CN)6]
 Thus this type o isomerism is caused by interchange of ligand between the two
complex ions.
Stereo isomerism
In coordination compounds the ligands are arranged in space in specific orientations around a
given metal atom or ion. Some common examples are represented in the Figs given below.
Cl H3N NH3
M M
Cl Cl
Cl
TETRAHEDRAL H3N NH3
SDQUARE PLANAR
NH3
H3N NH3
H3N NH3
NH3
OCTAHEDRAL
Space isomerism arises on account of the different positions and arrangements of

ligands (atoms or groups) in space around the metal ion.
It is two types:
 Geometrical isomerism
 Optical isomerism
 Geometrical or Cis -Tran isomerism :
 The types of isomerism occur in heteroleptic complexes due to different possible geometric ar-
rangements of the ligands.
 When two identical groups (ligands) occupy adjacent positions, the isomer is called cis and
when arranged opposite to one another, isomer is called Trans.
 This isomerism is not possible for complexes what coordination number 2 and 3.
 Tetrahedral complexes with coordination number 4 because in the four positions are equiva-
lent.
 Square planar complexes (Coordination number =4). Representing the central metal
atom by M and unidentate by A, B, C, D etc the square planar complexes may be
classified into the following different types.
 1. MA2B2 type e.g., [Pt (NH3)2 Cl2] i.e, Diamminedichloridoplatinum (II)
Cl NH3 Cl NH3
Pt Pt
Cl NH3 Cl
NH3
Cis – isomer Trans – isomer
(Similar groups on adjacent positions) (Similar groups on opposite positions)
A few other examples of this types include [Pd (NH 3)2 (NO2)2], [PtCl2 (py)2]
 2 MA2BC type e.g., [Pt(NH3) Cl (py)2]
NH3 Py Py NH3
Pt Pt
Cl Py Py
Cis – Cl Trans –
(Similar groups on adjacent positions) (Similar groups on opposite positions)
 3 M(AB)2 type: (in which AB represent an unsymmetrical didentate ligand) e.g.,

[Pt(gly)2] where gly = NH2CH2COO- called glycinato.
H2N O NH2
NH2 O
H2C C CH2
CH2
H2C Pt
C Pt
C
C
O O
O
H2N O
O O
Cis – diglycinatoplatinum (II) Trans – diglycinatoplatinum (II)
 4 M ABCD type: Square planar complexes of the type MABCD form three iso-
mers. Their structures may be obtained by fixing the position or one ligand e.g., A,
and placing at the trans position and one of the remaining three ligands one by one.
A C A B A B
M M M
D B D C C D
Two of these are cis and one is Trans.

i. Square planar complexes of the type MA4, MA3B and MAB3 do not shown geo-
metrical isomerism because in any of these case, the possible spatial arrange-
ments are equivalent.
ii. Tetrahedral complexes also do not show geometrical isomerism for the same
reason i.e relative positions of the ligands attached to the central metal atom is
same with respect to each other.
 Octahedral complexes (Coordination number = 6)
These may be classified into following different types:
 1 MA4B2 ro MA2B4 type. An example of this types is [Cr(NH3)4 Cl2]+ ion or
[Co(NH3)4Cl2]+ ion the cis and trans isomers of the s complex are represented below:
Cl Cl
H3N Cl H3N NH3
Cr Cr
H3N NH3 NH3

H3N
NH3 Cl
Cis-(Violet)
Trans – (green)
 2 [M(AA)2 B2] or [M (AA)2BC] type, i.e., containing one symmetrical bidentate

ligand (AA) and the other two unidentate ligand may be same or different, e.g.,
[CoCl2(en)2]+ ion exists in two geometrical isomers as shown below:
Cl Cl
Cl
en CO en CO
en
en
Cis – form Cl
Trans – form
 3 MA3B3 type. An example of the type MA3B3 is [CrCl3 (py)3] its cis and trans
isomers may be represented as following.
Cl Py
Cl Py Py Cl
Cr Cr
Py Cl
Cl Cl
Cl Py
Cis – or fac – isomer
Trans – or mer isomer
In cis form, similar groups (trio o donor atoms) occupy adjacent positions at the comes of
one of the octahedral faces and hence is called ro face – isomer while in trans form, the posi-
tions of trio of donor atoms are around the meridian of the octahedron. Hence it is called me-
ridional ro mere isomer.
Some other examples of this type are [Co(NH3)3 Cl3] and [Co(NH3)3 (NO2)3]
 Octahedral complex of the types or [MA6] or [MA5B] would not show geometrical
isomerism .
 Octahedral complex of the type [MABCDEF], i.e having all the six different uniden-
tate ligands form 15 different geometrical isomers. The only complex of this type pre-
pared so far is [Pt (NH3) (Br) (Cl) (I) (NO2) (py)]
 Optical Isomerism :
 Optical isomers rotate plane of polarised light in opposite directions – the two isomers are structur-
ally non – superimposable mirror image of each other (just as in the organic chemistry).
 They do not possess the plane of symmetry.
 The molecules or ions which are non-superimposable mirror image of each other are called chiral
and this property is called chirality.
 The optical isomers are called dexotro and laevo (d and l ) depending upon the direction in which
plance of the polarised light is rotated (i.e towards right or left).
 The d and l isomers of a compound are called enantiomers or enantiomorphism. Optical isomerism
is common in octahedral complexes with coordination number six involving 1,2 or 3 symmetrical
bidentate ligands (i.e ligand attached to the central atom be two coordinate bonds).
Thus on the basic the octahedral complexes showing optical isomerism may classified into follow-
ing different types:
 1. [M (AA)3 ] types i.e. containing three symmetrical bibentate ligands, e.g.,
[Co(en)3]3+ [Cr(OX)3]3- their dexotro and laevo form are represented below:
en en
en Co Co
en
en
MIRROR en
[Co(en)3]3+ (dexotro) [Co(en)3]3+ |(laevo)
ox ox
ox Cr Cr
ox
ox
MIRROR ox
3-
[Cr(ox)3] (dexotro) [Cr(ox)3]3- |(laevo)
 2. [M(AA)2 B2] or [M (AA)2 BC] type, i.e containing twp. symmetrical bibentate
ligands, e.g., [CoCl2 (en)2]+
 trans isomer does not shown optical isomerism since it is symmetrical while cis iso-
mers shown optical isomerism as it is unsymmetrical.
Cl + Cl +
en CO en CO
en en
Cl Cl
MIRROR
Trans [COCl2]+(en)2]+ISOMER - - OPTICALLY INACTIVRVE

(Superimposable mirror images)
Cl + Cl +
Cl
en CO CO
en
en en
Cl Cl
MIRROR
Trans [COCl2]+(en)2]+ ISOMER - - OPTICALLY INACTIVRVE

(Superimposable mirror images)
 3. [M(AA) B2 C2] type , Containing one symmetrical bidentate ligand e.g., [Co(en) (NH3)2Cl2]
its two optical isomers may be represented as followed:
Cl Cl
Cl Cl
en CO CO
en
NH3 H3N
NH3 NH3
Dextro MIRROR Laevo
Bonding in Coordination compound

Werner was the first to describe the bonding features in coordination compounds. But the the-
ory could not answer basic questions like:
 Why only certain elements form coordination compounds ?
 Why coordination compounds have directional properties?
 Why coordination compounds have characteristic magnetic and optical properties?
 Valence Bond Theory (VBT) : According to this theory,

 The metal atom in under the influence of ligands can use its (n-1)d, ns & np or ns np & nd or-
bitals for hybridisation to yield a set equivalent energy orbitals of definite geometry such as oc-
tahedral, tetrahedral, square plan are and so on these hybridised orbitals are allowed to overlap
with ligands orbitals that can donate electron pairs for bonding.
 It usually possible to predict the geometry of complex form the knowledge of its magnetic
behaviour on the basis of the valence bond theory.
 In the diamagnetic octahedral complex, [Co(NH3)6]3+ the cobalt ion is in +3 oxidation state
and has the electronic configuration 3d5.
Orbitals of Co3+ ion
↑↓ ↑ ↑ ↑ ↑
4s 4p
d2sp3 hybridised orbitals of Co3+
↑↓ ↑↓ ↑↓
[Co (NH3)6]3+ d2 sp3 hybrid

(inner orbital or low spin complex)
↑↓ ↑↓ ↑↓
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
Six pairs of electrons
from six NH3 molecules
The complex [Co(NH3)6]3+ is called as inner orbital or low spin or spin paired complex.
 The paramagnetic octahedral complex, [CoF6]3- uses outer orbitals (4d) in hybridisation (sp3d2)
 it is thus called outer orbital or high spin or spin complex;
Orbitals of Co2+ ion
↑↓ ↑ ↑ ↑ ↑
2 3 3+
d sp hybridised orbitals of Co 4s 4p 4d
↑↓ ↑ ↑ ↑ ↑
3-
[CoF6] 3d Sp3 d3 hybrid 4d
(Outer orbital or high spin complex)
↑↓ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
3d Six pairs of electrons
OTHER EXAMPLES : from six F-ion
4d
Orbitals of Ni3+ ion ↑↓ ↑↓ ↑↓ ↑ ↑

3d 4s 4p
3 2+
sp hybridised orbitals of Ni
↑↓ ↑↓ ↑↓ ↑ ↑
3d
[NiCl4]2- Sp3 hybrid
(High spin complex) ↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓

Four pairs of electrons
form 4 Cl-
In tetrahedral complexes one s and three p orbitals are hybridised to form equivalent orbitals
oriented tetrahedral. Each Cl-1 ion donates a pair of electrons. The compound is paramag-
netic since it contains two unpaired electrons.
 Similarly [Ni(CO)4] has tetrahedral geometry but is diamagnetic since nickel is in
Zero oxidation state an contains no unpaired electron.
 In the square planar complexes, the hybridisation involved is dsp 2. An example is
[N i(CN)4]2-. Here is in +2 oxidation state and has the electronic configuration 3d8.
The hybridisation:
Orbitals of Ni2+ ion ↑↓ ↑↓ ↑↓ ↑ ↑

3d 4s 4p
3 2+
dsp hybridised orbitals of Ni
↑↓ ↑↓ ↑↓ ↑↓
3d 4s
[Ni (CN)4]2- Dsp2 hybrid
(Low spin complex) ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Four pairs of electrons 4s
form 4 CN- groups
Each of the hybridised orbitals receives a pair of electrons from a cyanides ion. The com-
pound is diamagnetic due to absence of unpaired electron.
Some exceptions(of VBT) of magnetic property :
 [Mn(CN)6]3- has magnetic moment of two unpaired electrons.
 [Fe(CN)6]3- has a paramagnetic moment of five unpaired electrons.
 [CoF6]3- is paramagnetic with four unpaired electrons while [Co(C2O4)3]3+ is dia-
magnetic.
 This apparent anomaly is explained by valence bond theory in terms of formation of
inner orbital and outer orbital coordination entities.
 [Mn(CN)6]3-, [Fe(CN)6]3- and [Co(C2O4)3]3- are inner orbital complexes involv-
ing d2 sp3 hybridisation, here former two complexes are paramagnetic and the
latter diamagnetic.
 [MnCl6]3- , [FeF6]3- and [COF6]3- are outer orbital complexes involving sp3 d2
hybridisation and are paramagnetic corresponding to four, five and four un-
paired electrons.
Ni2+ ion ↑↓ ↑↓ ↑↓ ↑ ↑
(Ground state) 3d 4s 4p
Square planer diamag- ↑↓ ↑↓ ↑↓ ↑↓

2+
netic complex of Ni
dsp2Hyhdridisation
 Thus, we may wrongly assume that all the square planer complexes of Ni(II)
should be diamagnetic.
 This is actually not so.
 Some square planar complexes of Ni (II) are known which are paramagnetic.
 In these cases, we are assuming that one of the unpaired 3d electrons is excited to
4p orbitals that two unpaired electrons are present as shown below:
4s 4p
↑↓ ↑↓ ↑↓ ↑ ↑
Ni2+ ion
dsp2Hyhdridisation
(Excited state)
 Valence bond theory cannot explain as to why excitation occurs in one square
planer complex but not in the other.
 Similarly, in the case of the complex [Cu(NH3)4]2+ it cannot explain why excita-
tion of one 3d electron into 4p orbital takes place.
 Limitations of Valence Bond Theory :
While the VB theory, to a large extent, explains the formation, structures and magnetic
behaviour or coordination compounds. It suffers from the following shortcomings:
 It involves a number of assumptions.
 It does not given quantitative interpretation of magnetic data.
 It does not explain the colour exhibited by coordination compounds.
 It does not give quantitively interpretation of the thermodynamic or kinetic stabilities
of coordination compounds.
 It does not make exact predictions regarding the tetrahedral and square planar struc-
tures of 4- coordinate complexes.
 It does not distinguish between weak and strong ligands.
Crystal Field Theory(CFT)
 It is based upon electro-static interactions between the metal ion and the ligand.
 Ligands are treated as point charges in case of anions or dipoles in case of neutral
molecules.
 The five d orbital in isolated gaseous metal atom/ ion have same spherically field or
negative charges surround the metal atom / ion.
 However. When the negative filed is due to ligands (either anions or the negative
ends of dipolar molecules like NH3 and H2O) in a complex it becomes asymmetrical
and the degeneracy of the d orbitals is lifted.
 It results in splitting or the d orbitals.
 The pattern or splitting depends upon the nature of the crystal field.
1. Crystal field splitting in octahedral coordination entities:
 In an octahedral coordination entity with six ligands surrounding the metal atom/ion
ON THE AXES.
 There will be repulsion between the electron in metal d orbitals and the electrons (or
negative charges) of the ligands.
 Such repulsion is more when the metal d orbital is directed towards the ligands than
when it is away from the ligands.
 Thus the dx2 - y2 and dz2 orbital which point towards the axes along the direction of
the ligand will experience more repulsion and will be raised in energy.
 The dxy, dyz and dzx orbitals which are directed between the axes will be lowered
in energy relative to the average energy in the spherical crystal field.
 Thus the degeneracy of the d orbitals has been removed due to ligands electron –
metal electron repulsions in the octahedral complex to yield three orbitals of lower
energy, t2g set and two orbitals of higher energy eg set.
 This splitting of the degenerate levels due to the presence of ligands in a definite ge-
ometry is termed as crystal field splitting and the energy separation is denoted by ∆0
(CFSE) (the subscript so is for octahedral ).
 The energy of the two eg orbitals will increases by (3/5)∆0 and that of the three t2g
will decrease by (2/5)∆0.
 The crystal filed splitting, ∆0 depends upon the filed produced by the ligand and
charge on the metal ion.
 Some ligands are able to produce strong fields, in which case, the splitting well be
large whereas other produce weak fields and consequently result in small splitting or d
orbitals.
 Orbitals in general, ligands cab be arranged in series in the order of increasing filed
strength as given below:
I-< Br-< SCN-<Cl-< S2-< F-< OH-< C2O42-< H2O < NCS-<edta4-<NH3< en < CN-< CO
dx2-y2dz2
eg
3/5 ∆0
Energy State II Average energy level
∆0
(Bari centre)
Average energy of d – orbitals in a 2/5 ∆0
spherical crystals field
State I t2g
dxydyzdzx
d – Orbitals in free ion Splitting of d – orbitals in an
octahedral crystal field
 Such a series is termed as spectrochemcial series.

 It is an experimentally determined series based on the absorption of light by com-
plexes with different ligands.
 Let us assign electrons in the d orbitals or metal ion in octahedral coordination enti-
ties.
 The single d electron occupies one of the lower energy t2g orbitals.
 In d2 and d3 coordination entities the d electron occupy the t 2g orbitals. in single in ac-
cordance with the Hand’s rule.
 For d4 ions two possible patterns of electron distribution arise;
 (i) the fourth electron could enter the t2g level and pair with an existing electron.
 Or
 (ii) it could avoid paring by occupying the e g. Level.
 which of these possibilities occurs depends on the relative magnitude of the crystals
field splitting ∆0 and the paring energy, P [P represents the energy required for elec-
tron pairing in a single orbital) the two options are:
 (i) If ∆0 < P : the fourth electron enters one of the e g orbitals giving the configura-
tions t2g3 eg1.
 Ligands for which ∆0 <P are known as weak filed ligands and form high spin com-
plexes.
 Hence the complex is known as : weak filed -high spin complexes.
 (ii) If ∆0 > P : it becomes more energetically favourable for the fourth electron to
occupy a t2g orbital with configuration t2g4 eg0 orbitals.
 It gives which produce this effect are known as strong filed ligands and form low
complexes.
 Hence the complex is known as : strong filed -low spin complexes.
 Calculations shown that d3 to d7 coordination entities are more stable for stronge
filed as compared to weak filed field cases.
Crystal field splitting in tetrahedral coordination entities :

 In tetrahedral coordination entity formation.
 The d orbital splitting is inverted and it smaller as compared to the octahedral filed
splitting.
 For the same metal the same ligands and metal ligand distances it can be shown
that ∆t = (4/9) ∆0.
 Consequently. The orbital splitting energies are not sufficiently large for forcing
pairing and therefore low spin configurations are rarely observed.
dxydyzdxy
2/5 ∆t t2
Energy ∆t
Average energy of d – orbitals in a 3/5 ∆t
spherical crystals field dx2-y2dz2
e
d – Orbitals in free ion Splitting in a tetrahedral crystal field
Colour in Coordination Compounds

 The colour of the complex is complementary to that which is absorbed.
 The complementary colour is the colour generated from the wavelength left over.
 If green light is absorbed by the complex it appears red.
 If light corresponding to the energy of blue green region is absorbed by the complex.
It would excite the electron form t2g level to the eg level (t2g eg t2g eg) consequently
the complex appears violet in colour.
 The crystal field theory attributes the colour of the coordination compounds to
d- d transition of the electron.
Energy eg eg
hv
t2g t2g
ground state excited state
 It is important to note that in the absence of ligand, crystal field splitting does not
occur and hence the substance is colourless, e.g. removal of water from [Ti(H-
2O)6]Cl3 on heating renders it colourless.
 Anhydrous CuSO4 is white but CuSO4. 5H2O is blue in colour.

 The influence of the ligand on the colour of a complex may be illustrated by consider-
ing the [Ni(H2O)6]2+ which forms when nickle chloride is dissolved in water.
 If the didentate ligand, Ethane 1,2 diamine , (en) is progressively added in the molar
ratio of en : Ni.= 1:1, 2:1, 3:1 the following series of reactions and their associated
colour changes occur:
[Ni(H2O)6]2+ (aq) + en (aq) = [Ni(H2O)4(en)]2+(aq) + 2H2O
Green pale blue
[Ni(H2O)4 (en)] (aq) + en (aq) = [Ni(H2O)2(en)2]2+ (aq) + 2H2O
2+
Blue / purple
[Ni(H2O)2 (en)2] (Aq) + en(aq) = [Ni(en)3]3-
2+
+ 2H2O
Violet
Colour of Some Gem Stones
 Ruby is aluminium oxide (Al2O3) containing about 0.5-1% Cr3+ ion (d3). Which are
randomly distributed in positions normally occupied by Al 3+ .d – d transitions at
these centres give rise to the colour.
 In emerald Cr3+ ions occupy octahedral sites in the mineral beryl (Be3Al2Si6O18) the
absorption band seen in the ruby shift to longer wavelength, namely yellow – red
and blue. Causing emerald to transmit light in the green region.
 Limitations of Crystal Field Theory :
 The crystal filed model is successful in explaining the formation, structures, colour and magnetic
properties of coordination compound to a large extent.
 however it assumes that the ligands are point charges.
 The anionic ligands should exert the greatest splitting effect, but anionic ligands actually are found
at the low end of the spectrochemcial series.
 Further it does not takes into account the covalent character of bonding between the ligands and
the central atom.
 These are some of the weaknesses of CFT. Which are explained by ligand filed theory (LET) and
molecular orbital theory.
 Bonding in Metal Carbonyls :
 The homolptic carbonyls (compounds containing carbonyl ligands only) are formed by most of the
transition metals.
 These carbonyls have simple, well defined structures, tetracarbonylnickel (0) is tetrahedral, and
pentacarbonyliron (0) is trigonal-bipyramidal while hexacarbonly chromium (0) is octahedral.
 Decacarbonyldimanganese is made up of two square pyramidal Mn (CO)5 units joined by a

Mn- Mn bond.
 Octacarbonyldicobalt (0) has a CO – CO bond bridged (BRIDGE BOND) by two Co groups
CO CO
OC CO
Ni Fe
OC CO OC
CO CO
Ni(CO)4 tetrahedral Fe(CO)5
Trigonal bypyramicdal
CO
CO CO CO CO CO CO
Cr
OC Mn Mn CO
CO
CO
CO CO CO
CO CO
Cr(CO)6 octahedral
[Mn2(CO)10]
CO CO CO
OC
Co Co Structures of some representative ho-
CO molptic metal carbonyls.
OC OC CO
[Co2(CO)8]
π π
C≡O
M δ
Synergic bonding
 Synergic Bonding :
 The metal carbon bond in metal carbonyls possess both s and p character.
 The M – C bond is formed by the donation of one pair of electrons on the carbonyl carbon into
vacant d- orbitals of the metal.
 The M – C π bond is formed by the donation of a pair of electrons form a filled d orbital of
metal into the vacant anti bonding π orbital of carbon monoxide.
 The metal to ligands bonding creates a synergic effect which strengthens the bond be-
tween CO and metal
 Stability of coordination compounds :
 The stability of a complex in solution refers to the degree of association between the two spe-
cies involved in the state of equilibrium.
 The magnitude of the (stability of formation) equilibrium constant for the association, quntitia-
tively expresses the stability, if we the reaction of the type:
M + 4L ⇆ ML4
 Then the large the stability constant the higher the proportion of ML 4 that exists
In solution.
M + L ⇆ ML K1 = [ML] /[M][L]
ML + L ⇆ ML2 K2 = [Ml2] /[ML] [L]
ML2 + L ⇆ ML3 K3 = [ML3] /[ML2][L]
ML3 + L ⇆ ML4 K4 = [ML4] /[ML3][L]
 Where K1, K2, etc, are referred to as stepwise stability constants. Alternatively, we
can write the overly stability constant thus:
M + 4L ⇆ ML4 β4 = [ML4] /[M][L]4
The stepwise and overly stability constant are therefore related as follows:
β4 = K1×K2 ×K3 × K4
or more generally.
β n = K1×K2 ×K3 × K4 ……… Kn
 but mostly 1/ βn i.e. INSTABILITY CONSTANT or Dissociation constant of a
complex compound is calculated.
 So , larger the the instability constant – lesser the stability of a complex com-
pound.
 USES :
1. The colour reactions given by metal ion with a number of ligands (especially chela-
tion ligands), as a result of formation of coordination entities, form the basis for
their detection and estimation. Examples of such reagents include EDTA. DMG
(dimethylglyoxime) etc.
2. Hardness of water is estimated by simple titration with Na2EDTA. The Ca2+and
Mg2+ ion form stable complexes with EDTA. The selective estimation of these
ions can be done due to difference in the stability constant of calcium and mag-
nesium complexes.
3. Some important extraction processes of metals, like those of silver and gold, make
use of complex formation. Gold for examples. Combines with cyanide in the
presence of oxygen and water to form the coordination entity [Au(CN)2]- in
aqueous solution. gold can be separated in metallic form this solution by the ad-
dition of zinc.
4. Similarly, purification of metal can be achieved through formation and subse-
quent decomposition of their coordination compound. For examples, impure
nickel is converted to [Ni(CO)4]. This is decomposed to yield nickel.
5. The pigment responsible for photosynthesis chlorophyll, is a coordination com-
pound of magnesium.
6. Haemoglobin, the red pigment of blood which acts as oxygen carrier is a coordi-
nation compound of iron.
7. Vitamin B12 - Cyanocobalamine. The anti-anaemia factor is a coordination com-
pound of cobalt.
8. Coordination metal ions are the enzymes like carboxypeptidase A and carbonic an-
hydrase (catalysts of biological systems).
9. Coordination compound are used as catalysts for many industrial processes, exam-
ples include rhodium complex [(Ph3P)3RhCl] a Wilkinson’s catalyst , is used for
the hydrogenation of alkenes.
10. Articles can be electroplated with silver and gold much more smoothly and evenly
from solutions of the complexes, [Ag(CN) 2]- and [AU(CN)2]- than form a solution
of simple metal ions.
11. In black and white photography, the developed film is fixed by washing with hypo
solution which dissolves the unrecompensed AgBr to form a complex [Ag(S 2O3)2]3-
.
12. The excess of copper and iron are removed by the chelating ligands D – Penicil-
lamine and desferrioxme B via the formation of coordination compounds.
13. EDTA is used in the treatment of lead poisoning as it makes a soluble coordina-
tion compound with Pb deposited in the tissue which can be excreted from the
body.
14. Some coordination compounds of platinum effectively inhibit the growth of tu-
mours. Examples are; cis plating and related compounds.

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CHEMISTRY BY: T.K.

 [The whole thing written in square bracket]

 Naming of (IUPAC) Coordination Compounds

 [Ag(NH3)2] [Ag(CN)2] is named as:

 [Pt(NH3)4 Cl2] Br2 and [Pt(NH3)4 Br2 ]Cl2

Pentaamminenitrito-O-cobalt (III) Pentaamminenitrito-N-cobalt (III)

Some other examples are

Space isomerism arises on account of the different positions and arrangements of

 3 M(AB)2 type: (in which AB represent an unsymmetrical didentate ligand) e.g.,

Two of these are cis and one is Trans.

H3N NH3 NH3

 2 [M(AA)2 B2] or [M (AA)2BC] type, i.e., containing one symmetrical bidentate

Trans [COCl2]+(en)2]+ISOMER - - OPTICALLY INACTIVRVE

Trans [COCl2]+(en)2]+ ISOMER - - OPTICALLY INACTIVRVE

Bonding in Coordination compound

 Valence Bond Theory (VBT) : According to this theory,

[Co (NH3)6]3+ d2 sp3 hybrid

Orbitals of Ni3+ ion ↑↓ ↑↓ ↑↓ ↑ ↑

(High spin complex) ↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓

Orbitals of Ni2+ ion ↑↓ ↑↓ ↑↓ ↑ ↑

(Low spin complex) ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Square planer diamag- ↑↓ ↑↓ ↑↓ ↑↓

 Such a series is termed as spectrochemcial series.

Crystal field splitting in tetrahedral coordination entities :

Colour in Coordination Compounds

 Anhydrous CuSO4 is white but CuSO4. 5H2O is blue in colour.

 Decacarbonyldimanganese is made up of two square pyramidal Mn (CO)5 units joined by a

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