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Basic Concept

Simple salts Molecular or additional compounds

When solutions containing two or more salts in

When an acid reacts with an alkali, neutralization
stoichiometric (i.e., simple molecular) proportions
takes place and a simple salt is produced,
are allowed to evaporate, we get crystals of
NaOH + HCl  NaCl + H2O
compounds known as molecular or addition
When dissolved in water, these salts ionize and
compounds. These are of two types depending on
produce ions in solution. Depending upon the
their behaviour in aqueous solution.
extent of neutralization of the acid or base, these
may be normal, acid or basic salts. Mixed salts
contain more than one acidic or basic radicals, e.g.,
Double Salt Coordination Compounds.
Addition compounds are formed when stoichiometric amounts of two or more stable compounds join together. For
KCl + MgCl2 + 6H2O  KCl.MgCl2.6H2O
K2SO4 + Al2(SO4)3 + 24H2O  K2SO4 . Al2(SO4)3 . 24H2O
(potassium alum)
CuSO4 + 4NH3 + H2O  CuSO4 . 4NH3 . H2O
(tetrammine copper (II) sulphate monohydrate)
Fe(CN)2 + 4KCN  Fe(CN2) . 4KCN
(potassium ferrocyanide)
Double salts or Lattice Compounds Coordination Compounds

Those which lose their identity in solution (double Those which retain their identity in solution
salts) (complexes)
When crystals of carnallite are dissolved in water, When the other two examples of coordination
the solution shows the properties of K+, M2+ and compounds dissolve they do not form simple ions –
Cl–, ions. In a similar way, a solution of potassium Cu2+, or Fe2+ and CN– but instead their complex ions
alum shows the properties of K+. Al3+ and SO42– remain intact. Thus the cuproammonium ion
ions. These are both examples of double salts [Cu(H2O)2(NH3)4]2+ and the ferrocyanide ion
which exist only in the crystalline state. [Fe(CN)6]4– exist as distinct entities both in the solid
and in solution. Complex ions are shown by the use of
square brackets.
 Double salts and mixed salts. Mohr salt, FeSO4 . (NH4)2SO4 . 6H2O is a double salt.
Bleaching powder, CaOCl2 is a mixed salt. It is a salt of Ca2+ in which the anions present are Cl– and OCl–.
Similarly, NaKSO4 is a mixed salt in which there are two cations Na+ and K+ and one anion SO 24 .
Basic Definition
Werner’s Theory
In his coordination theory Werner introduced two great ideas :
(1) In a coordination complex a metal ion is engaged in strong binding with a certain number of neutral and/or
anionic groups in the first sphere of attraction, now called the coordination zone or sphere;
The metal ion is surrounded by the neutral and/or anionic groups in the coordination zone in a definite geometrical
Werner was able to explain the natural of bonding in complexes, and he concluded that in complexes the metal
shows two different sorts of valency:
1. Primary valencies. These are non-directional. The modern explanation would be as follows. The complex
commonly exists as a positive ion. The primary valency is the number of charges on the complex ion. In
compounds, this charge is matched by the same number of charges from negative ions. Primary valency
applies equally well to simple salts and to complexes. Thus in CoCl 2 (Co2+ + 2Cl–) there are two primary
valencies, i.e. two ionic bonds. The complex [Co(NH3)6]Cl3 actually exists as [Co(NH3)6]3+ and 3Cl–.
Thus the primary valency is 3, as there are three ionic bonds.
2. Secondary valencies. These are directional. In modern terms the number of secondary valencies equals
the number of ligand atoms coordinated to the metal. This is now called the coordination number.
Ligands are commonly negative ions such as Cl–, or neutral molecules such as NH3. Less commonly,
ligands may be positive ions such as NO+. Each metal has a characteristic number of secondary valencies.
Thus in [Co(NH3)6]Cl3 the three Cl– are held by primary valencies. The six NH3 groups are held by
secondary valencies.

CoCl3.6NH3  3AgCl
CoCl3.5NH3  2AgCl
CoCl3.4NH3  1AgCl
Formulae of some cobalt complexes

Old New
CoCl3.6NH3 [Co(NH3)6]3+ 3Cl–
CoCl3.5NH3 [Co(NH3)5Cl]2+ 2Cl–
CoCl3.4NH3 [Co(NH3)4Cl2]+ Cl–

Co2O3 + NH3 + KCl Co(NO3)3.6NH3 + AgCl

(heat) AgNO3

conc. moist.
HCl +Co(SO4). 6NH3 Co Cl3 6NH3 Co(OH)3.6NH3+AgCl
H2SO4. Ag2O

KI conc.HCl
. .
Co I3. 6NH3 +KCl No change
The neutral molecules or ions (usually anions) which are linked directly with the central metal atom/ion are called
ligands. In most of the complexes, ligands act as donor of one or more lone pairs to the central metal atom/ion. It
should be noted that in metallic carbonyls, the ligand, CO, acts as both donor and acceptor (M  CO).

Number of sigma coordinate bonds attached to the central metal ion or atom. For example, in
[Fe(CN6)]4–, the coordination number of Fe2+ ion is 6.
The central metal ion and the ligands that are directly attached to it, are enclosed in a square
bracket, called coordination sphere or first sphere of attraction.
Sidgwick extended the Lewis theory to account for the bonding in the coordination
compounds. He introduced the term coordinate bond for a shared electron pair, if it initially
belonged to one atom (donor atom) only. In this case, the donor atom acts as a Lewis base
and the metal ion acts as a Lewis acid. The metal ion accepts the electron pairs till it achieves
the next inert gas configuration. This is called the effective number rule.
The total number of electrons, which the central metal atom appears to possess in the
complex, including those gained by it in bonding, is called effective atomic number of
central metal ion. When the EAN was 36 (Kr), 54 (Xe) or 86(Rn), the EAN rule was said to
be followed.
For example, in [CO(NH3)6]3+ cobalt has an atomic number 27. In Co3+
number of electrons is 24. Each ammonia molecule donates a pair of
electrons. So, EAN becomes 24 + (2 × 6) = 36.
In many cases it was found EAN in a complex should be equal to number of
electrons present in next noble gas.
There are exceptions as well. For example,
EAN of [Ni(NH3)6]+2 is 38 and [Cr(NH3)6]3+ is 33.
The EAN of metals in some metal complexes
Metal complex Atomic number of Electrons on metal Electrons donated EAN
metal ion by the ligands
[Co(NO2)6]2+ Co (27) 24 6 x 2 = 12 24 + 12 = 36
[Cd(NH3)4]2+ Cd(48) 46 4x2=8 46 + 8 = 54
[PtCl6]2– Pt(78) 74 6 x 2 = 12 74 + 12 = 86
[Cr(CO)6] Cr(24) 24 6 x 2 = 12 24 + 12 = 36
[Ni(CO)4] Ni(28) 28 4x2=8 28 + 8 = 36
[Ag(NH3)2]Cl Ag (47) 46 2x2=4 46 + 4 = 50
K4[Fe(CN)6] Fe (26) 24 6 x 2 = 12 24 + 12 = 36
[Cu(NH3)4]SO4 Cu(29) 27 4x2=8 27 + 8 = 35
K2[Ni(CN)4] Ni (28) 26 4x2=8 26 + 8 = 34
K2[PtCl6] Pt (78) 74 6 x 2 = 12 74 + 12 = 86
K3[Cr(C2O4)3] Cr (24) 21 6 x 2 = 12 21 + 12 = 33
K2[HgI4] Hg (80) 78 4x2=8 78 + 8 = 86
Use of Sidgwick theory or Effective number rule to calculate number of ligands.
This rule can be used, to some extent, to calculate the number of ligands
(especially CO) attached to a metal atom or ion. This is because carbonyls, in
general, obey E.A.N. rule. This application is illustrated by the following
Calculate the number of CO ligands that can be attached to Ni, [At. No. of Ni =
28]. At. no. of next noble gas, Kr = 36
 No. of electrons to be provided by ligands = 36—28 = 8
As each CO provides two electrons, no. of CO groups that will be attached to Ni
= 8/2= 4
 Formula of complex compound formed – [Ni(CO)4]
(ii) Calculate the value of (x) in the carbonyls HxCr(CO)5 [At. no. of Cr = 24]
Electrons from 5 CO groups = 5  2 = 10
At. no. of Kr (next noble gas) =36
 No. of (1 electrons to be provided by H-atoms, x = 36–(24 + 10) = 2
 Formula of the complex compound formed is H2Cr(CO)5.
Q. The coordination number and the oxidation state of the
element ‘E’ in the complex [E(en)2 (C2O4)] NO2 (where (en) is
ethylene diamine) are, respectively (AIEEE 2008]
(a) 6 and 2 (b) 4 and 2
(c) 4 and 3 (d) 6 and 3
Ans en, C H 2  NH 2 is bidentate ligand
CH 2  NH 2
C 2O 24  is also bidentate ligand
Hence, coordinating head are six
(en : 2 × 2 = 4 + (ox) 2)
Coordination number 6
Complex can be ionized as
[E (en)2 (C2O4)] NO2  [E (en)2 (C2O4)+ NO 2 oxidation number x = 0 + (–2) = + 1
Q. The coordination number of central metal atom in a complex is determined by
(a) the number of ligands around a metal ion bonded by sigma bonds
(b) the number of ligands around a metal ion bonded by pi bonds
(c) the number of ligands around a metal ion bonded by sigma and pi bonds both
(d) the number of only anionic ligands bonded to the metal ion
Ans. Coordinate number is the maximum covalency shown by a metal or metal ion. It is the maximum number
of ligands attached to metal by sigma or coordinate bonds.
Q. One mole of the complex compound Co(NH3)Cl3, gives 3 moles of ions on dissolution in ater. One
mole of the same complex reacts with two mole of AgNO3 solution to yield two moles of AgCl(s).
The structure of the complex is
(AIEEE 2003)
(a) [Co(NH3)5Cl] Cl2 (b) [Co(NH3)3Cl3[.2NH3
(c) [Co(NH3)4Cl2]Cl.NH3 (d) [Co(NH3)4Cl]Cl2. NH3
Ans. [Co(NH3)5Cl] Cl2 [Co( NH3 )5 Cl]2   2Cl 

three ions

2Cl   2Ag  
 2AgCl
2 mol 2 mol 2 mol
Based on donor and acceptor properties ligands may be of the following types:

(1) With one (or more) lone (2) Without a lone pair of electrons but with -
pair (s) of electrons bonding with -bonding electrons e.g. : ethylene,
benzene, cyclopentadienyl ion.

(a) No vacant orbitals to receive (b) Vacant orbitals that can be used to receive
back donated electrons from metal back donated  electrons from the low
e.g.: H2O, NH3, F– oxidation state metal e.g. : PR3, CN–, CO
Ligands may also be classified according as the number of coordination positions they occupy around the metal
ion. A ligand having only one lone pair of electrons can only be bonded to a metal ion at just one stereochemical
point, that is, it occupies one coordination position only. This is called a unidentate or a monodentate ligand. When
the ligand can occupy two positions around the metal ion it is di(bi) dentate; with three, four, five or six such links
the ligands are called tri (ter) denate, (tetra) quadridentate, penta (qunique) dentate or (hexa) sexa dentate

Ligand type Name Formula

Didentate Ethylenediamine (en) CH2


Biguanide (Hbig)
Glycinate ion (gly)

Bipyridine (bpy)

(o-phen) (phen) N N
Oxalate ion (ox) Oxalate ion (ox)

Tridentate Diethylenetriamine (dien)

Tridentate Diethylenetriamine (dien)
(Terdentate) (Terdentate)

Iminodiacetate ion (ida) Iminodiacetate ion (ida)

(CH2)2 NH (CH2)2 NH

Tetradentate Triethylenetetramine
(Quadridentate) (trien) NH2 NH2 (CH2)2

anion (salen) O CH2

Some authors prefer to classify ligands according to the number of donor atoms they can offer to metal ions. Thus,
when a ligand has two atoms which can simultaneously serve as donors it is called didentate and so on. It follows
that a didentate ligand has to have two lone pairs, a tridentate three lone pairs and so on. The polydentate ligands
may be further subdivided according to the nature of their donor centres. Thus ethylendiamine is a didentate ligand
with two neutral donors (N) whereas oxalate ion is didentate with two acidic (anionic) donors (O –). Glycinate ion is
again a didentate with one neutral donor (N) and an acidic donor (O–). Such discussions may be extended to other
polydenates as well.

A chelating ligand is one that contains two or more donor centres so disposed that they can simultaneously occupy
more than one position around the same metal ion in the first sphere of coordination(A chelating ligand offers more
than one sigma-electron pair donor groups to the same metal ion.) The resulting complexes are called metal
chelates. Thus all polydentate ligands, when bonded to the same metal ion, are also chelating ligands. A chelating
ligand must possess two or more lone pairs such distance apart that it may form suitable strain-free raings at the
metal on. Too small-sized and too large-sized rings are unsuitable for stable binding. Usual strain-free rings are
5— or 6— membered ones. 4— and 7— membered chelate rings are also known but are less stable than 5— or
6— membered ones.
A bridging ligand is one that can simultaneously bond itself to more than one metal ion. OH, Cl –, NH2– etc.
can function as monodentate and also as bridging ligands. A bridging ligand must have at least two lone pairs so
that it can get linked to at least two metal ions. Hydrazine, NH 2—NH2, can serve as a monodentate and as a
bridging ligan but not as a chelating ligand because a 3-membered ring will be too strained to be stable, Part II).
A flexidentate ligand is one that can chelate a metal ion in more than one way. For example cysteine,
HS—CH2—CH(NH2)—COOH can function as a tridentate (SNO) and as a didentate in three ways again (SN; NO;
The most important tetradentate ligands are the -
many ‘biological’ macrocyclic ligands, such as
porphyrin and its derivatives and a host of similar
molecules that can be readily synthesised. N N


Hexadentate ligands: The most common example
for a hexadentate ligand is the EDTA (ethylene HOOCH2C N
diamine tetra acetic acid). CH2COOH
 Flexidentate character: Polydentate ligands are said to have flexidentate character if they do not use all its
donor atoms to get coordinated to the metal ion e.g., EDTA generally act as a hexadentate ligand but it can
also act as a pentadentate and tetradentate ligand
 Certain polydentat ligands have flexidentate character e.g., EDTA generally act as a hexadenate ligand
but it can also act as a pentadentate or a tetradentate ligand.
 In complex compounds the central metal atom or ion can act as Lewis acid and ligands as Lewis bases.
 Transition metal can form complexes in the zero, positive and low negative oxidation states i.e., the centre
of co-ordination can be a neutral atom, cation or an anion in low negative oxidation state
 Chelating ligands is a neutral molecule, free radical or ion (cation or anion) with two or more lonepairs
of electrons on different atoms.
Chelates with five membered rings are very sable if these do not contain a double bond e.g., in
ethylenediamine. However, chelates with six membered rings are very stable if the ligands contain double
bond e.g., acac.
 Macrocyclic effect: This term refers to the greater thermodynamic stability of a complex with a cyclic
polydenate ligand when compared to the complex formed with a non-cyclic ligand.
e.g., Zn(II) complex with ligand;

 -acid ligand: Ligands which are capable of accepting an appreciable amount of -elecron density from the
metal atom into empty  or * orbital of their own are called -acceptor or -acid ligands e.g., CO.
Certain ligands like NO can act as a neutral as well as unipositive (NO+) ligand. In such case it is very
difficult to find the oxidation state and the charge on the ligand from the given formula of the complex. For
example, in the complex [Fe(H2O)5NO]2+ Fe is in +1 oxidation state with five H2O neutral ligands and one
Unipositive NO+ ligand. During the formation of this complex, NO gives its unpaired electron to Fe2+ and change it
into Fe+. Another example of this type is the complex nitroprusside ion,[Fe(CN) 5NO]2–, in which Fe is in +2
oxidation state with five CN– ligands and one NO ligand.
Similarly, NO2 canbe a uninegative ligand (nitrito O– – N = O or –N ). or a positive ligand (NO 2 ).
In such cases, the experimentally observed magnetic moment of the complex in solid state can decide the oxidation
state of the central metal ion. From it, nature of the ligand can be decided.

 Chelating rings form more stable complexes than monodentate ligands. This is because replacing
monodentate ligands by chelating ring is a process in which entropy increases e.g.,
[Co(H2O)6]2+ +3en   (Co(en)3]2++ 6H2O
 Ligands with more than six donor atoms or larger groups form unstable ring. This is due to the steric
 Chelates with five membered rings including the metal atom are more stable if these do not contain a
double bond. On the other hand chelates with six membered rings are more stable if the ligands contain
conjugated double bonds e.g., acetyl acetonato complexes.

The central atoni in a complex compound or ion can be even a non-metal e.g., in Ba[BrF4]2 central atom in
complex ion is Br

The following rules are used when naming coordination compounds.

 If a coordination compound is ionic the name of cation is given first followed by the name of anion. The
names of cation and anion are separated by a space.
 Within a complex ion, ligands are named first followed by the metal ion. And no space are left between
parts of the name of same coordiantion entity.
 Ligand names are listed in alphabetical order (numerical prefixes indicating the number of ligands are not
considered in determining that order.
Example: 1. [CoCl(NH3)5]Cl2 (pentaamminechloridocobalt(2+) chloride)
2. [AuXe4]2+ (tetraxenonidogold(2+)
 The oxidation number of the central atom is shown by Roman numeral in bracket immediately following
its name but only if the oxidation state can be defined without ambiguity.
 Alternatively, the charge on a coordiantion entity may be indicated in Arabic numbers with the number
preceding the charge sign and enclosed in bracket.
Example: K4[Fe(CN)6]
potassium hexacyanidoferrate(II), or
potassium hexacyanidoferrate(4–), or tetrapotassium hexacyanidoferrate
 Complex positive ions and neutral coordination compound have no special ending but complex negative
ions always end in the suffix ate. In most of the cases, the suffix –ate is fixed to English names of the
metals but in some cases –ate is fixed with Latin names of metal
Example: K3[Fe(CN)5NO] Potassium pentacyanidonitrosylferrate( II)

Element Metal as named in anionic complex

Cobalt Cobaltate
Nickel Nickelate
Chromium Chromate
Iron Ferrate
Copper Cuprate
Silver Argenate
Lead Plumbate
Note: In the case of mercury we may use both mercurate and hydrazinate.
 The name of the neutral coordination compound is given in one word only as the name of Ni(CO)4 is
tetracarbonylnickel (O)
 Name of the Ligands
(i) Anionic ligands ending with ‘ide’ ‘ite’ or ‘ate’ are named by replacing the final ‘e’ by ‘O’
giving ‘ido’, ‘ito’ and ‘ato’ respectively.
Formula Ligand name
1. Cl– chlorido
2. CN – cyanido
3. H– hydrido
4. D– or 2H– deuterido or [2H]hydrido
5. PhCH2CH2Se– 2-phenylethaneselanolato
6. MeCOO– acetato or ethanoato
7. Me2N dimethylazanido or dimethylamido
8. MeCONH2 acetamide (not acetamido)
9. MeCONH– acetylazanido or acetylamido (not acetamido)
10. MeNH2 methanamine
11. MeNH– methylazanido or methanaminido
12. MePH2 methylphosphane
13. MePH– methylphosphanido
14. MeOS(O)OH methyl hydrogen sulfite
15. MeOS(O)O– methyl sulfito, or methoxidodioxidosulfato(1-)
Note: (i) In its complexes, hydrogen is always treated as anionic and named as Hydrido.
(ii) Names of neutral and cationic ligand names are used without modification (even if they carry
‘ide’, ‘ite’ or ‘ate’)
(iii) Prefixes di, tri, etc. are generally used for simple ligands. Enclosing marks are not required.
(iv) Prefixes bis, tris, tetrakis, etc. are used with complex expressions and when required to
avoid ambiguity. Enclosing marks be placed around the multiplicand.

Example: For example, one would use diammine, for (NH3)2, but bis(methylamine), for (NH2Me)2.
Formulae of Coordination Compounds
The following rules are used when formulating coordination compounds.
(i) The central atom is listed first.
(ii) The ligands are then listed in alphabetical order. If an abbreviation is used in a formula to represent a ligand,
the first letter of the abbreviation is used to determine the position of the ligand in the alphabetical list.
(iii) The formula for the entire coordination entity, whether charged or not, is enclosed in square brackets.
When ligands are polyatomic, their formulae are enclosed in parentheses. Ligand abbreviations are also
usually enclosed in parenthese.
(iv) There should be no space between representations of ionic species within a coordination formulae.
(v) If the formula of a charged coordination entity is to be written without that of the counter-ion, the charge is
indicated outside the square bracket as a right superscript, with the number before the sign.
(vi) The oxidation number of a central atom may be represented by a Roman numeral, which should be placed
as a right superscript on the element symbol.
1. [Co(NH3)6]Cl3
hexaamminecobalt(III) chloride
2. [CoCl(NH3)5]Cl2
pentaamminechloridocobalt(2+) chloride
3. [CoCl(NH3)4(NO2)]Cl
tetraamminechloridonitrito-κN-cobalt(III) chloride
4. [PtCl(NH2Me)(NH3)2]Cl
diamminechlorido(methanamine)platinum(II) chloride
5. [CuCl2{O=C(NH2)2}2]
6. K2[PdCl4]
potassium tetrachloridopalladate(II)
7. K2[OsCl5N]
potassium pentachloridonitridoosmate(2_)
8. Na[PtBrCl(NH3)(NO2)]
sodium amminebromidochloridonitrito-κN-platinate(1_)
9. [Fe(CNMe)6]Br2
hexakis(methyl isocyanide)iron(II) bromide
10. [Co(en)3]Cl3
tris(ethane-1,2-diamine)cobalt(III) trichloride
 Transition metals can form complexes both in zero, positive and also in low negative oxidation states.
For example,
[ Ni(CO) ] 4 K [Fe(CN) ]
3 6 Na[Co(CO) ] 4
tetracarbony ln ickel ( 0 ) potassium hexacyanoferrate ( III ) sodium tetracarbonylcobaltate ( 1)

 The name of a complex compound should not start with a capital letter e.g.,
[Cu ( NH 3 ) 4 ]SO 4
tetraam min ecopper ( II ) sulphate
and not Tetraam min e copper ( II ) sulphate

 The full name of the complex should be written as one word without any gap.

 In optical isomers, the designation ( + ) and (–) or (d) and (?) are put before the complete formula of the
complex compound and not before the complex ion showing optical isomerism
e.g., (+) – K3 [Cr(C2O4)3] and not K3 (+) – [Cr(C2O4)3]
Q. The IUPAC name for the complex [Co(NO2)(NH3)5]Cl2 is (AIEEE 2006)
(a) nitrito-N-pentamminecobalt (III) chloride
(b) nitrito-N-pentamminecobalt (II) chloride
(c) pentammine nitrito-N-cobalt (II) chloride
(d) pentammine nitrito-N-cobalt (III) chloride
Ans. [Co( NO3 ) ( NH 3 )5 ]Cl 2
Pentam min e nitrito  N  cobalt ( III) chloride
Q. The IUPAC name of the coordination compound K3 [Fe(CN)6 is (AIEEE 2005)
(a) tripotassium hexacyanorin (II)
(b) potassium hexacyanoferrate (III)
(c) potassium hexacyanoferrate (III)
(d) potassium hexacyanoferrate (II)
Ans. K3 [Fe(CN )6 ]
cation anion
Oxidation state of Fe in anion = + 3
Q. Write the IUPAC name for [Cr(NH3)5CO3]Cl
[IIT 1996]
Ans. Pentaamminecarbonatochromium(III) chloride.
Q. Write the formulae of the following complexes.
[IIT, July 1997]
(i) Pentamminechlorocobalt (III) ion
(ii) Lithium tetrahydridoaluminate (III)
Ans. (i) [Co(NH3)5Cl]2+; (ii) Li[AlH 4]
Q. Write the IUPAC name of this compound [Cr(NH3)5(NCS)][ZnCl4].
Is this compound coloured?
[IIT, May, 1997]
Ans. Pentammineisothiocyanatochromium (III) tetrachlorozincate (II).
Compound will be coloured because Cr (III) has d3 configuration and
so d–d transition is possible.
Q. Write IUPAC names of the following compounds :
[IITQuali. 1995]
(i)[Co(NH3)5ONO]Cl2 ; (ii) K3[Cr(CN)6]
Ans. (i) Pentaamminenitrito-O-cobalt (III) chloride.
(ii) Potassium hexacyanochromate (III)