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coordination theory

coordination theory

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study material for iit jee student

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Published by: SLEVINPJOY on Aug 16, 2009
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IIT-JEE
CHEMISTRY
P. JOY
CO-ORDINATION CHEMISTRY
E D U C A T I O N S
,
608-A, TALWANDI KOTA (RAJ.) Ph. 0744 - 2405510CO-ORDINATION CHEMISTRYPAGE # 1
MEMORY MAP
CO-ORDINATION CHEMISTRY 
IonisationisomerismLinkageisomerismHydrateisomerismCoordinationisomerismLigandisomerismPolymerisationisomerismCoordinationpositionisomerismGeometricalOpticalCo-ordinationcompoundLigandsMonodentateBidentateNegativeBridgingPolydentatePositiveAmbidentateChelatingLabileMetal CarbonylsBasic theoryWerner theoryStructuralNomenclatureIsomerismStability ConstantBondingVBTC.T
 
CationicComplexesAnionicComplexesNeutralComplexesBridigingComplexesStereooisomerismNeutral
 
IIT-JEE
CHEMISTRY
P. JOY
CO-ORDINATION CHEMISTRY
E D U C A T I O N S
,
608-A, TALWANDI KOTA (RAJ.) Ph. 0744 - 2405510CO-ORDINATION CHEMISTRYPAGE # 2
 
DEFINITIONS
(1)Simple Salts :
When an acid reacts with an alkali, neutralisation takes place and a simple salt isproduced,NaOH + HCl
NaCl + H
2
OWhen dissolved in water, these salts ionise and produce ions in solution. Mixed salts contain more thanone acidic or basic radicals, e.g. NaKSO
4
.
(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 asmolecular or addition compounds. These are of two types depending on their behaviour in aueoussolution.
(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 individualcomponents of the double salts do.eSO
4
.(NH
4
)
2
SO
4
.6H
2
O
e
2+
(aq) + 2NH
4+
(aq) + 2SO
42
(aq) + 6H
2
OMohr's saltK
2
SO
4
.Al
2
(SO
4
)
3
.24H
2
O
2K
+
(aq) + 2Al
3+
(aq) + 4SO
42
(aq) + 24H
2
OPotash alumIn 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 e(CN)
2
and KCN are mixed together and evaporated, potassium ferrocyanide, e(CN)
2
4KCN is obtained which inaqueous solution does not give test for the e
2+
and CN
ions, but gives the test for K
+
ion andferrocyanide ion, e(CN)
64
. The ions [e(CN)
6
]
4
is called
complex ion
& K
+
is called
counter ion.
e(CN)
2
+ 4KCN
e(CN)
2
.4KCN
l
4K
+
+ e(CN)
64
Thus we see that in the molecular compound like e(CN)
2
. 4KCN, the individual compounds losetheir 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 metalatom 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 K
4
[e(CN)
6
], or(ii)A complex cation and a simple anion such as [Cu(NH
3
)
4
]SO
4
(iii)A complex cation and a complex anion such as [Co(NH
3
)
6
][Cr(C
2
O
4
)
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 areenclosed 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
.
 
IIT-JEE
CHEMISTRY
P. JOY
CO-ORDINATION CHEMISTRY
E D U C A T I O N S
,
608-A, TALWANDI KOTA (RAJ.) Ph. 0744 - 2405510CO-ORDINATION CHEMISTRYPAGE # 3
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 metalion is shown by dotted lines.(b)
Secondary or auxiliary valency :
It is also termed as coordination number (usually abbreviatedas CN) of the central metal ion. It is non-ionic or non-ionisable (i.e. coordinate covalent bond type). Thisis 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 secondaryvalencies since in every case the fulfilment of coordination number of the central metal ion appearsessential.(3)The ions attached to primary valencies possess ionizing nature whereas, the ions attached to secondaryvalencies 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. Theprimary 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 circumscribedabout the metal ion. or metals having four co-ordination number, the four valencies are either arrangedin a square planar or tetrahedral nature.

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