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Coordination Compound Slide-01

Coordination compounds are complex molecules formed by metal atoms bound to anions or neutral molecules through electron sharing, playing crucial roles in biological systems such as haemoglobin and chlorophyll. The document discusses the theory of coordination compounds proposed by Alfred Werner, detailing concepts like primary and secondary valences, coordination numbers, and various types of ligands. It also covers the naming conventions for these compounds as per IUPAC rules.

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0% found this document useful (0 votes)
4 views67 pages

Coordination Compound Slide-01

Coordination compounds are complex molecules formed by metal atoms bound to anions or neutral molecules through electron sharing, playing crucial roles in biological systems such as haemoglobin and chlorophyll. The document discusses the theory of coordination compounds proposed by Alfred Werner, detailing concepts like primary and secondary valences, coordination numbers, and various types of ligands. It also covers the naming conventions for these compounds as per IUPAC rules.

Uploaded by

adarsh4554439292
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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The complex compounds in which the metal atoms are bound to a number of

anions or neutral molecules by sharing of electrons, such compounds are


called coordination compounds.

 These compounds play a vital role in our lives.


 Haemoglobin of blood and chlorophyll of plants are coordination
compounds of Fe and Mg respectively.
 vitamin B12 is coordination compound of cobalt.

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[CHEMISTRY] 11-09-2022 1
Alfred Werner was the first scientist to formulate ideas about the
structures of coordination compounds.

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According to the above observation together with the result of
conductivity measurement, Werner in 1898 proposed his theory of
coordination compounds.

Electrical conductance of complexes : More the number of ions provided


greater is the electrical conductance of the complex in aqueous medium.
Electrical Conductivity ∝ Number of ions
Example:
The electrical conductance of aqueous solutions of:
[Fe(NH3)5Cl]Cl2 < [Fe(NH3)6]Cl3

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1. In coordination compounds metals show two types of valences-primary
and secondary.
2. The primary valences are normally ionisable and are satisfied by
negative ions.
2. The secondary valences are non ionisable. These are satisfied by neutral
molecules or negative ions.
3. The secondary valence is equal to the coordination number and is fixed
for a metal.
4. The ions/groups bound by the secondary linkages to the metal have
characteristic spatial arrangements corresponding to different
coordination numbers.

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Primary valencies Secondary valencies

(i) Equal to oxidation state of CMA (i) Equal to coordination number of CMA

(ii) Satisfied by anions (ii) satisfied by ligands

(iii) Non directional (iii) Directional

(iv) Ionisable (iv) Non-ionisable

(v) not helpful geometry predictions (v) helpful in geometry predictions

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Fe(NH3)6Cl3  [Fe(NH3)6]Cl3

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Fe(NH3)5Cl3  [Fe(NH3)5Cl]Cl2

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Molecular or Addition Compounds
When two or more simple salts are chemically combined together in fixed
proportion by weight the molecular or addition compounds are formed.

K2SO4 + Al2(SO4)3 + 24H2O  K2SO4. Al2(SO4)3 .24H2O


Alum

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Double Salt or Lattice Compounds:
The addition compounds which loose their identity in aq.
solution and get completely ionised in water.

(i) K2SO4.Al2(SO4)3.24H2O (Potash Alum)

(ii) FeSO4(NH4)2SO4.6H2O (Mohr's salt)

(iii) KCl.MgCl2.6H2O (Carnallite)

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Coordination or Complex Compounds
Those molecular or addition compounds which retain their identity
in aq. solution or do not loose the identity of constituents are called
complex salt.
Example:
K4[Fe(CN)6](aq)  [Fe(CN)6]4- + 4K+

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(a) Complex ion:
An aggregate of metal ion with anions, cation or neutral molecules is
called as complex ion.
Central Metal Ion
(i) The metal ion which forms complex ion in combination with anions,
cation or neutral molecules is called as central metal ion.
(ii) Central metal ion acts as an electron pair acceptor and forms
coordinate covalent bond.

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(c) Coordination Number
The total number of coordinate covalent bonds formed by central metal
ion with ligands is called as coordination number.
In case of monodentate ligands,
C.N. = No. of ligands

In case of polydentate ligands:


C.N. = No. of ligands x denticity

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(d) Coordination sphere:
The neutral molecule or anions [ligands] which are directly bonded
to the central metal ion are known as coordination sphere.
The coordination sphere is generally expressed by enclosing in
square bracket [ ].

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(e) Counter ion:
The ionisable group which are written outside the bracket and are
called “counter ion.”
Example: [Co(NH3)6]Cl3

Counter ion

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(f) Coordination polyhedron
The spatial arrangement of the ligand atoms which are directly
attached to the central atom/ion defines a coordination polyhedron
about the central atom.
The most common coordination polyhedra are octahedral, square
planar and tetrahedral.

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(g) Oxidation number:
It is a number which represents the electrical charge on the
central metal atom of a complex ion.
(h) Homoleptic complexes:
Complexes in which a metal is bound to only one kind of donor
groups, are known as homoleptic complexes.
e.g., [Co(NH3)6]3+,

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Heteroleptic complexes:
Complexes in which a metal is bound to more than one kind of donor
groups, are known as heteroleptic.
e.g., [Co(NH3)4Cl2]+

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(i) Ligands
The ions or molecules bound to the central atom/ion in the
coordination entity are called ligands.
They act as electron pair donor (Lewis bases).

Naming of ligands
(i) o-suffix is provided to the name of anionic ligands.
(ii) ium-suffix is provided to the name of cationic ligands

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On the basis of denticity
Denticity: It represents the number of coordination bonds the ligand
can form with some metal cation.
1. Monodentate ligands:
The ligand which has only one donor site is called a monodentate
ligand.
Example: NH3, H2O, O2, etc.

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NH3 ammine
H2O aqua
NO nitrosyl
PH3 Phosphine
PPh3 Triphenyl phosphine
O2 dioxygen
N2 dinitrogen
CH3-OH methyl alcohol
CH3-NH2 methyl amine
NH2CONH2 urea
NH2NH2 hydrazine
CH3-O-CH3 dimethyl ether
CO carbonyl
CS thiocarbonyl

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O2+ oxygenium

NO+ nitrosylium or nitrosonium

NO2+ nitronium

H2N - +NH3 hydrazinium

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Ligands Name
F- fluorido/fluoro
Cl- chlorido/chloro
Br- bromido/bromo
I- iodido/iodo
O-2 oxido/oxo
S-2 sulphido/sulpho
OH- hydroxido/hydroxo
CH3-O- methoxido/methoxo
O2- superoxido/superoxo
O2-2 peroxido/peroxo
N-3 nitrido
N3- azido
(NH2)- amido
NH-2 imido
H- hydrido

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When a ligand can bind through two donor atoms the ligand is said
to be didentate ligand.
Example:
H2NCH2CH2NH2 (ethane-1,2-diamine)
C2O42– (oxalate)

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When several donor atoms are present in a single ligand the ligand
is said to be polydentate.
Example- Ethylenediammine tetra acetate ion

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Ligand Name Denticity

Ethylene diammine tetra acetic


[H4EDTA] 2
acid

[H3EDTA]- Ethylene diammine acetato 3

[H2EDTA]-2 Ethylene diammine di acetato 4

[HEDTA]-3 Ethylene diammine tri acetato 5

[EDTA]-4 Ethylene diammine tetra acetato 6

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Ligands which have two different donor atoms but at the time of
coordination can donate electron pair from any one donor atoms
are called ambidentate ligand.
Example:
M -C≡N cyanido (CN)
M N≡C- isocyanido(NC)

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Flexidentate ligands :
Ligands which can change their denticity are called flexidentate
ligands.
Example-

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Bidentate or polydentate ligands which attach themselves with
central metal ion in such a way that they form a ring, are known as
chelating ligands.
More the number of chelate rings, more is the stability of complex.
Stability of complex ∝ No. of chelate rings.
Chelate effect: The stabilization of coordination compounds due to
chelation is known as chelate effect.

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Ligand which donate electron pair to central metal ion & form
coordinates bond but simultaneously they accept electron pair
from central metal ion through back bonding or synergic bonding.
Example:
CO, NO+, CN-, R3P, R3As etc.

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Q.1. CN- is ambidentate ligand because
(1) it has multiple bonds
(2) carbon as a negative charge
(3) it form chelate
(4) both C & N can donate lone pair

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Q.2. Coordination number of Co in [CoF6]-3 is
(1) 4 (2) 5 (3) 6 (4) 8
Q.3. The neutral ligand is
(1) Chlorido (2) Hydroxido (3) Ammine (4) Oxalato
Q.4. H2N-CH2-CH2-NH2 serves as :
(a) Monodentate ligand (b) Chelating ligand
(c) Bridging ligand (d) Cationic ligand

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Labile complex:
Complexes in which the ligand substitution is fast are known as
labile complexes.
Inert complex:
Complexes in which ligand substitution is slow, are known as inert
complexes.

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This concept was proposed by Sidgwick. In a complex, the EAN of metal atom is
equal to the total number of electrons present in it.
EAN = Z – O.N. of metal + 2 * C.No.
Where, Z = atomic number of metal atom
O.N. = oxidation number of metal
C.No. = Coordination number of complex
An ion with central metal atom having EAN equal to next inert gas will be more
stable.

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Naming is based on set of rules given by IUPAC.
1. Name of the compound is written in two parts (i) name of cation, and (ii)
name of anion.
2. The cation is named first in both positively and negatively charged
coordination complexes.
3. The dissimilar ligands are named in alphabetical order before the name of
central metal atom or ion.
4. For more than one similar ligands, the prefixes di, tri, tetra, etc. are
added before its name. If the di, tri, etc. already appear in the complex
then bis, tris, tetrakis are used.
5. If the complex part is anion, the name of the central metal ends with
suffix ‘ate’.

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6. Names of the anionic ligands end in ‘0’, names of positive ligands
end with ‘ium’ and names of neutral ligands remain as such. But
exceptions are there as we use aqua for H2O, ammine for NH3,
carbonyl for CO and nitrosyl for NO.
7. Oxidation state for the metal in cation, anion or neutral
coordination compounds is indicated by Roman numeral in
parentheses.
8. The name of the complex part is written as one word.
9. If the complex ion is a cation, the metal is named same as the
element.
10. The neutral complex molecule is named similar to that of the
complex cation.

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Some examples are
(i) [Cr(NH3)3(H2O)3]Cl3
triamminetriaquachromium (III) chloride
(ii) [Co(H2CH2CH2H2)3]2(SO4)3
tris (ethane-l,2-diamine) cobalt (III) sulphate
(iii) [Ag(NH3)2] [Ag(CN)2]
diamminesilver (I) dicyanidoargentate(I)
(iv) K4 [Fe(CN)6]
potassium hexacyanidoferrate(II)

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 The formula of a compound is a shorthand tool used to provide basic
information about the constitution of the compound in a concise and
convenient manner.
 Mononuclear coordination entities contain a single central metal atom.

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The following rules are applied while writing the formulas:
 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
abbreviated ligand, the first letter of the abbreviation is used to
determine the position of the ligand in the alphabetical order.

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 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 parentheses. Ligand abbreviations are also
enclosed in parentheses.
 There should be no space between the ligands and the metal within a
coordination sphere.

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 When the formula of a charged coordination entity is to be written
without that of the counter ion, the charge is indicated outside the
square brackets as a right superscript with the number before the
sign.
 For example, [Co(CN)6]3–, [Cr(H2O)6] 3+, etc.
 The charge of the cation(s) is balanced by the charge of the anion(s).

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Q. Write the formulas for the following coordination
compounds:
(a) Tetraammineaquachloridocobalt(III) chloride
(b) Potassium tetrahydroxidozincate(II)
(c) Potassium trioxalatoaluminate(III)
(d) Dichloridobis(ethane-1,2-diamine)cobalt(III)
(e) Tetracarbonylnickel(0)

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Coordination compounds exhibit the following types of isomerism:
Structural Isomerism:
In this isomerism, the isomers have different bonding pattern. Different
types of structural isomers are:

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Linkage isomerism:
This type of isomerism is shown by the coordination compounds having
ambidentate ligands. e.g.,
Example: [Co(NH3)5(NO2)]Cl and [Co(NH3)5(ONO)]Cl
or pentaamminenitrito-N-Cobalt(III) chloride and pentaam minenitrito-O-
Cobalt (III) chloride.

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Coordination isomerism:
This type of isomerism arises from the interchange of ligands between
cationic and anionic complexes of different metal ions present in a
complex,
e.g., [Cr(NH3)6)][Co(CN)6] and [Co(NH3)6] [Cr(CN)6]

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Ionisation isomerism:
This type of isomerism arises due to exchange of ionisable anion
with anionic ligand.
 e.g..

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Solvate isomerism:
This is also known as hydrate isomerism. In this isomerism, water is
taken as solvent. It has different number of water molecules in the
coordination sphere and outside it. e.g..
 [Co(H2O)6]CI3,
 [Co(H2O)4C12]Cl·2H2O,
 [Co(H2O)3Cl3].3H2O

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Stereoisomers have the same chemical formula and chemical
bonds but they have different spatial arrangement. These are of
two types:
1. Geometrical isomerism
2. Optical isomerism

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Geometrical isomerism
Geometrical isomers are of two types i.e., cis and trans isomers. This
isomerism is common in complexes with coordination number 4 and 6.

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(i) Tetrahedral complexes do not show geometrical isomerism.
(ii) Square planar complexes of formula [MX2L2] (X and L are unidentate)
show geometrical isomerism.
Example:

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(iii) Square planar complex of the type [MABXL] (where A, B, X, L,
are unidentate ligands) shows three isomers, two cis and one trans.
e.g., [Pt(NH3)(Br)(Cl)(Py)].

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Octahedral complexes of formula [MX2L4], in which the two X ligands may
be oriented cis or trans to each other, e.g., [Co(NH3)4Cl2)+.

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Octahedral complexes of formula [MX2A2], where X are unidentate
ligands and A are bidentate ligand. form cis and trans isomers,
 e.g., [CoC12(en)2]+

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 In octahedral complexes of formula [MA3X3], if three donor atoms of
the same ligands occupy adjacent positions at the corners of an
octahedral face. it is known as facial (fac) isomer.
 When the positions are around the meridian of the octahedron, it is
known as meridional (mer) isomer.
 e.g., [Co(NH3)3(NO2)3]

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The compounds having same molecular formula but rotate the plane of
polarised light in opposite direction, are called optical isomers & the
phenomenon is known as optical isomerism.
 Dextrorotatory: The isomer which rotates the plane of polarised
light to the right is known as dextrorotatory.
 Laevorotatory: The isomer which rotates the plane of the
polarised light to the left is known as laevorotatory.

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Enantiomers: Optical isomers are mirror images that cannot be
superimposed on one another. These are called as enantiomers.

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Chiral Molecule: The molecules or ions that cannot be
superimposed are called chiral molecules.

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 Complexes of the types [M(aa)3] where aa is bidentate ligand exist
optical isomerism.
 Ex. [Co(en)3]Cl3

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 Complexes of the type [M(aa)2bc] or [M(aa)2b2] show optical
isomerism.
 Complexes of the type [M(aa)b2c2]
Ex. [CoCl2(en)(NH3)2]+

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 Werner was the first to describe the bonding features in coordination
compounds.
 But his theory could not answer basic questions like:
◦ Why only certain elements possess the remarkable property of forming
coordination compounds?
◦ Why the bonds in coordination compounds have directional properties?
◦ Why coordination compounds have characteristic magnetic and optical
properties?

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Many approaches have been put forth to explain the nature of bonding in
coordination compounds viz.

◦ Valence Bond Theory (VBT)

◦ Crystal Field Theory (CFT)

◦ Ligand Field Theory (LFT)

◦ Molecular Orbital Theory (MOT).

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This theory was proposed by L. Pauling in 1930s.
 According to this theory, when a complex is formed, the metal ion/atom
provides empty orbitals to the surrounding ligands.
 Coordination number shows the number of such empty orbitals, i.e., number
of empty orbitals is equal to the coordination number.
 These empty orbitals hybridised before participation in bonding and the
nature of hybridisation depends on the nature of metal and on the nature of
approaching ligand.

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Outer orbital complexes:
 When outer d-orbital are used in bonding, the complexes are called
outer orbital complexes.
 They are formed due to weak field ligands or high spin ligands and
hybridisation is sp3d2.
 They have octahedral shape.

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Inner orbital complexes
 When d-orbitals of (n–1) shell are used in bonding, the complexes are
known as inner orbital complex.
 They are formed due to strong field ligands or low spin ligands and
hybridisation is d2sp3.
 They are also octahedral in shape.

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