Chapter IV : complex in solution Dr : M.

LEMMOUCHI

Chapter IV:
COMPLEX IN
SOLUTION

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

I. Concept of a complex
I.1. Definition
A complex is a polyatomic structure MLnq soluble in water. The formula for a complex is
noted in square brackets, with the possible charge placed outside. For writing, we start with the
metal, the anionic ligands, neutral and finally the cationic ligands. Many complexes absorb part
of visible light: they are therefore colored. A complex is made up of:

►M: the central atom (ion) is the coordination center; The M are mainly the ions of transition
metals (block d), rarely those of group IA and IIA metals. The metal M has a vacant cell on its
valence layer.
The metal ion M is called a coordinator ion, if we have:
• 1 coordinator ion  mononuclear complex
• Several coordinating ions  polynuclear complex
►L: atoms, ions, molecules linked to M, are ligands or coordinates, L ligands are chemical
species having electrons to donate (atoms with free electron pairs, molecules with π electron:
anions).
Ligands are molecules or ions having at least one non-binding doublet (Lewis bases):

• L monodentates = only engages one bond like H2O, X-, OH-, etc.
• L bidentates = engage with two bonds with M as oxalate ion
•L Multi – Polydentates= engage several bonds (of several atoms) with the same metallic
center M like EDTA (Y4- ) (ethylene diamine tetra acetate ion).
►n: numbers of ligands attached to M; this is the coordination number NC= 2 to 12.
►q: the charge of the complex (The complex may be charged or not). The charge of a
complex is the sum of the charges brought by the metal ‘M’ and the ligands ‘L’.

I.2. The oxidation’s degree (number) of the central atom:

It is the charge should carry the metal if we removed all the ligands , with the free doublets
that they share with the metal center. It is represented by a Roman numeral.
The formal oxidation degree of the central metal, or STOCK number, is calculated by the
following formula:

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

Examples :

[Fe(CN)6] -3 : The total charge of this complex is : (-3)

Ligands (CN ): 6*(-1) = -6

The formal oxidation degree of the central metal is : O.D (Fe)  -6 + O.D (Fe) = -3 

O.D (Fe) = +3

In this complex, we are in the presence of iron at the formal oxidation state +3, denoted
Fe (III) or FeIII

[Cu(H2O)6] +2: The total charge of this complex is: (+2)

Ligands (H2O): 6*(0) = 0

The formal oxidation degree of the central metal is : O.D (Cu)  0 + O.D (Cu)= +2 

O.D (Cu) = +2

In this complex, we are in the presence of copper at the formal oxidation state +2, denoted Cu
(II) or CuII.

I.3. The number of ligands:

Indicated by the prefixes: di – tri- tetra- penta- hexa, hepta, octa, nona, etc. if the ligand is
monodentate and we use bis-triste-tetrakiste-pentakish-hexakis, etc; in the case of a
polydentate ligand.

I.4. Type of complexes:

a. Simple complex: the coordinator is only linked to the coordinator by a single band.

Example :PtCl62-, Ni(NH3)62+.

b. internal complexes or chelates: multi-dentate coordinator which contacts all its bonds
with the same coordinator ion

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

Example :

II. Nomenclature of coordination complexes

The rules below are issued by IUPAC (International Union of Pure and Applied Chemistry).
There are 3 types of the complex: neutral, cationic and anionic.
II.1. For the central atom:
The central atom is named last, the ligands appear in alphabetical order regardless of their
charge (charged complex). In case of doubling of vowels, either we use a separating hyphen,
or we practice elision.
II.2. For the ligands:
► We keep their usual name when they are neutral or cations

► We add the suffix 'O' to the root of its name when the ligand is anionic

► C5H5N pyridine = py

► CH3NH2 = Methylamine,

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

II.3. For the Metal:

For some metals, their Latin names are used if they are in anion complex :

B Borate Au Aurate
Ag Argentate Fe Ferrate
Pb Plombate Sn Stannate
Cu Cuprate
The name of a complex depends on its charge
► Negative charge (anionic complex): name of the ligand + name of the coordinator ion
(M) + suffix <<ATE >> + oxidation number of M (in Roman numerals) + Ion

Examples :
Fe(CN)63- : hexacyanoferrate(III) Ion.

[Fe(CN)5(CO)]3- : carbonylpentacyanoferrate (II) Ion.

[CoCl4]2- : tétrachlorocobaltate (II) Ion.

► Positive charge (cationic complex): name of the ligand + name of the coordinator ion
(M )+ oxidation number of M (in Roman numerals) + Ion .

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

Examples :

[Co(NH3)4Cl2] +: tetraamminedichlorocobalt (III) Ion

Cu(NH3)42+ : Ion tetra-amminecopper (II).

[Ag(NH3)2] + : diamminesilver (I) Ion

[Fe(NH4C5-C5NH4)3] 2+ : tris(bipyridine)iron (II) Ion

[Co(NH2CH2CH2NH2)2Cl2]+ : dichlorobis(ethylenediamine)cobalt (III) Ion

► neutral charge (neutral complex): name of ligand + name of coordinator ion M + oxidation
number of M (in Roman numerals)

Examples :

Fe(CO)5 pentacarbonyleIron

[Pt(NH3)BrCl(CH3NH2)]: amminebromochloromethylamineplatinum(II),

►For salt complex: or complex compounds which are composed of complex cation and
complex anion, the cation is named first then followed by the anion name.

Examples :

[Ag(NH3)2]Cl: diamminesilver(I) chloride,

Na3[AgF4] sodium tetrafluoroargentate(I)

K3[Fe(CN)6]: potassium hexacyanoferrate(III)

K4[Fe(CN)6] potassium hexacyanoferrate(II)

[Cu(NH3)4]SO4: tetraamminecopper(II) sulfate

[Co(NH3)6]Cl3: hexaamminecobalt(III) chloride

[Cr(NH3)6]3+ [CoF6]3-: hexaamminechromium(III) -hexafluorocobaltate(III)

[Pd(NH3)4]2+ [PdCl4]2- : tetraamminepalladium(II)-tetrachloropalladate(II)

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

REMARKS:

►There are many ligands which have two or more different donor atoms in their structure.
Such ligands can coordinate to the metal atom through any of their donor atoms and hence are
given different names corresponding to the nature of donor atoms linked to the metal atom.
Such compounds are called linkage isomers.

[Co(NH3)5(NO2)]Cl2 pentaamminenitrocobalt(III) chloride

[(Co(NH3)5(ONO)]Cl2 pentaamminenitritocobalt(III) chloride

NO2 - ion coordinated to the metal atom through the lone pair of electrons on negativelycharged
N atom, while ONO through the lone pair of electrons on negatively-charged on O atom.

-
SNC ion thiocyanato (through S)

-
NCS ion isothiocyanato (through N)

►To name bridging ligands between two metal ions, the prefix µ is used before the name of
each of the ligands.

[(NH3)4Co(OH)(NH2)Co(NH3)4] 4+: Octaammine-µ-amido-µ-hydroxodicobalt(III)

If a complex has two similar bridging ligands, µ-di is used for its name.

octaaqua-µ-di-hydroxodi-iron(III) sulphate

III. Overall dissociation reaction of the complex:

MLn(eq)  M(eq) + nL(eq)

In solution, a complex is always in equilibrium with the ions or molecules from which they are
formed. We can therefore write a balance equation expressing this balance.

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

The dissociation constant KD is the equilibrium constant of the dissociation reaction of the
complex. It is therefore defined in the equilibrium state. According to the relation of Guldberg
and Waage We also define KD:

pKD = -log (KD)

REMARK

The stability constant or formation constant βn is: βn = 1/KD.

The larger βn is, the more stable the complex is:

Properties :

► KD (and pKD) depend on the complex considered and the temperature.

► A complex is more stable if it is little dissociated, therefore the dissociation reaction is not
very advanced, therefore KD ↓ is small, and pKD ↑ big.

Examples :

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

IV. Successive constants of formations and dissociations

In the global equilibrium MLn  M + nL, n ligands are released by the MLn complex.

This reaction can be written as a series of successive equilibria in which a single ligand L is
released:

MLn  MLn-1 + L ; Kdn

MLn-1  MLn-2 + L ; Kdn-1

……
ML2  ML + L ; Kd2
ML  M + L ; Kd1
Each of the reactions MLi = MLi-1 + L is characterized by an equilibrium constant, denoted
Kdi and called the successive dissociation constant. According to the relationship of Guldberg
and Waage,

We also define pKdi = -log(Kdi).

We have the following relationships between the different equilibrium constants introduced:

n: the global formation constant (of the overall reaction)

Kfi: the partial formation constants (of each reaction)

KD: the overall dissociation constant (of the overall reaction)

Kdi: partial dissociation constants (of each reaction)

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

Examples

 Fe(C2O4)2-1 + (C2O4)2-2  Fe(C2O4)3-3 ; Kf3

 FeF4-  Fe3++ 4F- ; KD

 Zn(NH3)4 2+ Zn(NH3)3 2+ + NH3 ; Kd4

 Zn2+ + 4 NH3 Zn(NH3)4 2+ ; β4

V. Relationships between equilibrium constants

► we have : βn= 1/ KD et Kf1= 1/ Kd1 so :

βn= 1/ Kd1* 1/ Kd2* 1/ Kd3*……..*1/ Kdn  Log βn= Log ( 1/ Kd1* 1/ Kd2* .....*1/ Kdn)

Log βn= pKd1+ pKd2+……..+ pKdn  Log βn= ∑𝑛𝑖=1 𝑝𝐾𝑑𝑖

► β1=1/Kd1 et β2= Kf1* Kf2= 1/Kd1* 1/Kd2 β2= β1* 1/Kd2  Kd2= β1/ β2 

-log Kd2= -log β1/ β2  pKd2= log β2/ β1  pKdn= log βn/ βn-1

Except for : log β1= pKd1

VI. pKD scale (Prediction of the direction of L ligand exchange)

Consider the couples of the MLn/MLn-1; which participate in the exchange of a single ligand
(L).
The more βn is higher, the more metal (M ) is an acceptor of the ligand (L).
In other words, if pKd is higher so the metal is more an acceptor of the ligand L and if pKd is
lower , so the the complex ML is more donor of the L ligand.
The pKd scale diagram, the acceptor on the left and the donor on the right to predict the
exchange of the ligand, it is necessary to check the γ (gamma) rule (the acceptor of a pair 1
must have a pKd higher than that of the donor of a couple 2).

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

VII. Predominance diagram

Consider a solution containing the central metallic atom (or ion). The ligand L is gradually
added. The complexes ML, ML1, ….., MLn-1 are successively formed. We are interested in
the formation of the MLn complex.

Kdi= [MLi-1].[L]/ [MLi] log Kdi= log [MLi-1]/ [MLi]+ log [L] -log [L]= log Kdi+ log
[MLi-1]/ [MLi] pL= pKdi+ log [MLi-1]/ [MLi]

Note the analogy with the Henderson-Hasselbalch relationship for acid-base balances. By
reasoning on the previous relation, we have:

▪ If pL = pKdi  MLi = MLi-1

▪ If pL > pKdi  MLi < MLi-1

▪ If pL < pKdi  MLi > MLi-1

We represent these results on a predominance diagram.

The more pL increases, [L] decreases and the less the metal ion is complexed. The domain of
predominance of the metal cation corresponds to the highest values of pL.

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

▪ For pL > Kd : M> ML> M predominates ;

▪ For pL < Kd : M< ML< ML predominates.

We draw a predominance diagram along an axis graduated in pL, that is to say following the
decreasing ligand concentration:

More the stability is greater  the dissociation is more weaker 

the concentrations of the constituents is more lower  the complex
is more perfect

VIII. Factors influencing the stability of complexes

VIII.1. Internal factors

a. Nature of the coordinator ion

A complex is all the more stable if its coordinator ion has:

► Greater ionic valence

► Higher ionic valency.

►A greater electropositive (because Lewis acids: electronic doublet acceptor).

►Alkali metals do not give complexes.

►Transition metals give the most stable complexes.

b. Nature of coordination
Generally speaking, a complex is more stable if its coordinates are:

►Strong bases according to Lewis

► chelator: multi-dentate coordinate which contracts all its bonds with the same coordinator
ion.

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

VIII.2. Influence of pH on the stability of the complexes

Any ligand has acid-base properties: L is the base of an HL+/L couple.

Example: the NH3 ligand is the basis of the NH4+/NH3 couple.

The modification of the pH will therefore have an influence on the concentration of the complex
in solution.

Examples :

1. a complex with a basic ligand is completely destroyed in an acidic medium

Ag(NH3)2+  Ag+ + 2NH3 ; 1/β2 = 1/ 107.2

2* (H3O+ + NH3 → NH4++ H2O) ; (1/Ka)2 =( 1/10-9.2)2= 2.5*1018

Ag(NH3)2+ + 2 H3O+→ 2 NH4++ Ag++ 2 H2O : K= 1/β2* (1/Ka)2= 1.57*1011

The destruction of the [Ag(NH3)2+] complex by the addition of a strong acid is complete.

2. A weak acid becomes stronger by the complexation of its conjugate base.

Given the weak acid HCN, the dissociation of the acid in water is according to the following
reaction:

2* (HCN + H2O  CN- + H3O+ ); Ka2 = (10-9.3)2…..(1)

If we add, Ag+ to the solution there will be a complexation between CN- and Ag+ to form:

Ag+ + 2CN- → Ag(CN)2- ; β2= 1020.7……..(2)

Ag+ + 2HCN+ 2H2O → Ag(CN)2- + 2H3O+ ; K= β2. Ka2 = 1.25*102……(1+2)

After adding Ag+ to the HCN solution; Ag+ consumes CN- and shifts the equilibrium in the
direction of HCN acid dissociation, and if dissociation increases then the acid becomes stronger.

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

VIII.3. Dissolution of a precipitate by complexation:

Example: silver chloride in ammoniacal medium

If a sufficient quantity of aqueous NH3 is added to a precipitate of silver chloride AgCl, the
precipitate disappears by the formation of a complex ion (see chapter III [effect of complexation
on solubility])

The solubility of a species in solution can be greatly increased by the formation of a complex.
For example, there is competition between the formation of silver chloride (precipitate) and the
silver diammine ion (complex ion)

Ks is the solubility product in pure water, Ks= [Ag+]eq. [Cl-]eq= 10-9.75

β2= [Ag(NH3)2+]/ [Ag+].[NH3]2= 107.2 ………..(1)

When ammonia is added to a saturated AgCl solution, the overall reaction occurs:

In the presence of an excess of ammonia, the constant K being low, the equilibrium is little
shifted to the right; there is re-dissolution of AgCl following the formation of the diammine
silver (I) complex. We said that the complex mask the presence of AgCl.

AgCl(s)  Ag+ (aq) + Cl-(aq)

t=0 excess 0 0
t excess s′ s′

Ag+ (aq) + 2NH3 → Ag(NH3)2+

t s′ C0 0

teq ε C0- 2s′ s′

► At equilibrium we have: s′= [Ag+]+ [Ag(NH3)2+] …….(2)

► (1)  [Ag(NH3)2+]= β2 .([Ag+]. [NH3]2)

► (2) s′= [Ag+]+ β2 .([Ag+]. [NH3]2)= [Ag+].(1+ β2. [NH3]2)

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Chapter IV : complex in solution Dr : M. LEMMOUCHI

[Ag+]eq= s′/(1+ β2. [NH3]2) ………………………………….(3)

And like [Cl-]eq= s′ ……………………………………………………(4)

► Ks= [Ag+]eq[Cl-]eq= s′2/ (1+ β2. [NH3]2) s′= √Ks(1 + β2. [NH3]2)

Solubility is expressed by:

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