Effective Atomic Number (EAN) Rule

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 Effective Atomic Number Rule

• Sidgwich (1927) 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.
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 •The metal ion M accepts the electron pairs till it
achieves the next inert gas configuration.

•This is called the effective atomic number rule.

•The total number of electrons on the metal ion and

the electrons donated by the ligands is called the
effective atomic number (EAN), and when the EAN
was 36 (Kr), 54 (Xe), or 84 (Rn).
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 Metal Metal ion Electrons Electrons EAN
Complex with Z on metal donated by the
ion ligands

[Co(NO2)6]3- Co(27) 24 6x2= 12 36

[Cd(NH3)4]2+ Cd(48) 46 4x2= 8 54
[PtCl6]2- Pt(78) 74 6x2= 12 86
[(Cr(CO)6] Cr(24) 24 6x2= 12 36
[Fe(CO)5] Fe(26) 26 5x2= 10 36
[Ni(CO)4] Ni(28) 28 4x2 = 8 36
[Mn(CO)6]+ Mn(25) 24 6x2 = 12 36
[Co(CO)4Cl] Co(27) 26 5x2 = 10 36

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 [Co(CO)3(NO)] Co(27) 27 3x2 + 1x3 = 9 36
[Fe(CO)2(NO)2] Fe(26) 26 2x2 + 2x3 = 10 36
[Mn(CO)(NO)3] Mn(25) 25 1x2 + 3x3 = 11 36
[Mn(CO)5(C2H4)]+ Mn(25) 24 2x5 + 1x2 = 12 36
[Cr(C6H6)2] Cr(24) 24 2x6 = 12 36
[Fe(C5H5)2] Fe(26) 26 2x5 = 10 36
[Cr(NH3)6]3+ Cr(24) 21 6x2 = 12 33
[Mn(H2O)6)]2+ Mn(25) 23 6x2 = 12 35
[FeCl4]- Fe(26) 23 4x2 = 8 31
[Fe(CN)6]3- Fe(26) 23 6x2 = 12 35
[CoCl4]2- Co(27) 25 4x2 = 8 33
[Cu(NH3)4]2+ Cu(29) 27 4x2 = 8 35
[CuCl2]- Cu(29) 28 2x2 = 4 32
[AgX2]- Ag(47) 46 2x2 = 4 50
[Ni(C5H5)2] Ni(28) 28 2x5 = 10 38

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Note:
• The electrons donated by NO = 3, C5H5 = 5, C6H6 = 6.

• For transition metal complexes, the completed

valence shell electron configuration is
(n-1)d10ns2np6 (totaling 18 electrons for first row
transition metals) and so here the terminology
“Eighteen Electron Rule” is sometimes encountered.

• The opportunity of complexation provides added

stability so as to attain a pseudo-noble gas
configuration.
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• Here, the electron occupancy is confined to the
metal valence shell configuration only.

• The carbonyls, nitrosyls, pi-complexes and metal

complexes of allied ligand classes conform to EAN
rather remarkably.

• Random cases from coordination chemistry may be

examined for EAN conformity as in the examples
below:
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• In [Co(NH3)6]3+ since Co0 has a 3d74s24p0
configuration, then Co3+ contains 6 valence electrons.

• Since six NH3 or ligands furnish 12 electrons, then

attainment of EAN is achieved through metal
complexation.

• For Ni in [Ni(NH3)6]2+, The elemental configuration is

3d84s24p0 for Ni2+, and these eight valence electrons
plus 6 pairs from ligands (C.N 6) yield 20 valence shell
electrons.

• This is inconsistent with the EAN requirement.

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 Notes on First Raw Transition Metal Valence
Electronic Configuration

• This is generalized as 3dn4s2 (with 4p orbitals empty)

for elemental forms where n = 1 to 10.

• Cr (3d54s1) and Cu (3d104s1) are exceptions due to a

principle which prescribes better stability for
completely full or half-filled configurations.

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• Metals that do not attain the EAN of inert gas in
mononuclear carbonyls either dimerize as it is in
Co2(CO)8 and Mn2(CO)10 or form hydrido-or chloro-
carbonyls in which the M-oxidation state changes by
a unit.
• Pairing of electrons is through metal-metal bonds
and the compounds are diamagnetic

[Mn(CO)5Cl]

Cl
+.
+e-
Mn + 5CO [Mn(CO)5]
dim
[Mn(CO)5]-
25e- 10e- 35e- er
Mn2(CO)10
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• With Fe, Fe2(CO)9 and Fe3(CO)12 also form and
comply to EAN.

VERIFY THIS PLEASE!

• The only exception of a monomeric carbonyl not
obeying the EAN rule is [V(CO)6].

• This is due to instability (from steric hindrance or

overcrowding upon dimerisation) that would result
from change of C.N from six to seven.

• However, it is not as stable as other carbonyls and

readily accepts an electron giving [V(CO)6]-.

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Questions

1) Describe the Electroneutrality Principle.

2) Discuss the application of coordination chemistry in

daily life.

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 Note:

• The EAN is therefore an empirical rule of limited

predictive application say in the number of ligands
coordinated to the metal in the complex and
perhaps the likely geometry.

• Its usefulness in explaining other properties of

metal complexes is extremely restricted.

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 Stability of Coordination Compounds

• Because complexes are not generally prepared from

their components in the gaseous phase,
measurements of their stability necessarily imply a
comparison with the stability of some starting
material.

• The devastating majority of quantitative

measurements have been made in aqueous solutions
when the complex in question is formed by the
ligand displacing water from the aquo complex of the
metal ion.

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 • The term stability may take even further
connotations;

• A compound may be thermally stable yet react

violently with water at room temperature, i.e. be
hydrolytically unstable.

• The word ‘stable’ must always be qualified when

talking about a compound; on its own it raises the
immediate question:

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 Stable to what?
•This part therefore deals with thermodynamic
stability of complex ions in solution i.e.

•The extent to which the complex ion will tend to

be formed from, or dissociate into, its component
species when the system has reached equilibrium.

•The kinetic stability of complexes, i.e. the rate at

which the equilibria are reached will be discussed
later.
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 Stability constants

• When a metal ion reacts with a ligand in aqueous

solution, the step wise replacement of the
coordinated water molecules by the ligand occurs.

• By neglecting the charge for convenience, the first

step in the displacement of water molecules is:

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• If the equilibrium lies to the right we say a complex
has been formed (despite the fact that a complex
was already present to the left-hand side of the
equation).

• For convenience such equilibria are usually written

as:
M + L → ML
• Assume a unit activity coefficients for this
equilibrium, we can write:

K1 
ML
M L
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 • For the stepwise replacement of further water
molecules, we can write the stepwise equilibrium
constants as follows:

ML  L  ML 2 K2 
ML 2 
MLL
ML 2  L  ML 3 K3 
ML 3 
ML 2 L
ML 3  L  ML 4 K4 
ML 4 
ML 3 L

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• The equilibrium constants K1 to K4 for the formation
of complexes are called the stepwise formation
constants or stability constants.

• The numerical values decrease in the order

K1 > K2 > K3 > K4 > Kn

• The overall stability constant (β), is given as:

4 
ML4 
M L4

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• Therefore, an alternative way of expressing
formation constants is to represent the equilibria as:

M  L  ML 1 
ML 
ML
M  2L  ML 2 2 
 ML 2 
ML 2

M  3L  ML 3 3 
ML 3 
ML3
• And so on. It is readily apparent that:

β4 = K1 K2 K3 K4

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Or more generally

βn 
ML n 
ML n

Prove it!!!

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6/4/2020 23
• The overall stability (or formation) constant βn, can
clearly be expressed in terms of the stepwise
constants:

• These are thermodynamic constants which relate to

the system when it has reached equilibrium, and
must be distinguished from any considerations of
kinetic lability or inertness which refer to the speed
with which that equilibrium is attained.

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 Nomenclature

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• The naming of coordination compounds follows the
rules adopted by the International Union of Pure and
Applied Chemistry –IUPAC (1990).

• The most important rules, which find frequent use,

will be presented here.

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 IUPAC Nomenclature of coordination
compounds

(i) Writing the formulas of mononuclear (containing

single central metal atom) coordination compounds:

The central atom is listed first.

The ligands are then listed in alphabetical order
without considering their charge.

Polydentate ligands are also written alphabetically.

In case of abbreviated ligand, the first letter of

abbreviation is used to determine the position of ligand
in alphabetical order.
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 The formula of the entire coordination entity,
whether charged or uncharged, is enclosed in
square brackets.

When ligands are polyatomic, their formulas are

enclosed in parantheses.

Ligand abbreviations are also enclosed in

parantheses.

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, [Ag(NH3)2]2+, [Ni(NH3)6]2+, [Fe(CN)6]3–,

etc.

The charge of cation(s) is balanced by the charge

of anion(s).

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Thursday, June 4, 2020 30
 (ii) Writing the name of coordination compounds

The name of cation is written first in both positively

and negatively charged coordination entities followed
by the naming of anion.

The ligands are named in an alphabetical order

before the name of central atom/ion. (This procedure is
opposite to that in writing formula).

Names of anionic ligands and in-O, those of cationic

and neutral ligands are the same except aqua for H2O,
ammine for NH3, carbonyl for CO and nitrosyl for NO.
These are placed within closing marks [ ].
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 Note: IUPAC recommendations (2004)

The anion endings 'ide', 'ate' and 'ite‘ are changed

to 'ido', 'ato' and 'ito', respectively, when
generating the prefix for the central atom.

Prefixes mono, di, tri, etc., are used to indicate the

number of the individual ligands in the
coordination entity.

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 When the names of the ligands include a numerical
prefix, then the terms, bis, tris, tetrakis are used, the
ligand to which they refer being placed in
parenthesis.

For example, [NiCl2(PPh3)2] is named as

dichlorobis(triphenylphosphine) nickel (II).

Oxidation state of the metal in cation, anion or

neutral coordination entity is indicated by roman
numerical in parenthesis.
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 If the complex ion is a cation, the metal is named
same as the element. For example, Co in a complex
cation is called cobalt and Pt is called platinum.

If the complex ion is an anion, the name of the

metal ends with the suffix- ate. For example, Co in a
complex [Co(NH3)5Br]2- anion, is called cobaltate. For
some metals, the latin names are used in the
complex anions, e.g., ferrate for Fe.

The neutral complex molecule is named similar to

that of the complex cation.

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Question

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For Isomer complexes.
• Isomers are shown by the italicized prefixes followed by
a hyphen, e.g. cis-, trans-, fac-, mer-, dextro-, laevo-, etc.
examples are cis-[Pt(NH3)2Cl2] is cis-
Diamminedichloroplatinum(II),

• trans-[Co(NH3)4Cl2]Cl
Trans-Tetraamminedichlorocobalt(III) chloride,

• fac-[Ru(NH3)3(NO2)3]
fac- Triamminetrinitritoruthenium(III),

• (+)-[Co(en)3]3+
dextro-Trisethylenediamminecobalt(III).
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 • The linkage isomers for the ambidentate ligands are
distinguished by putting the symbol of the atom
that takes part in the coordination, e.g.
thiocyanato(N or S), nitrito(N or O).

Example:
• [(NH3)5Ru(NCS)]2+
Pentaamminethiocyanato(N)ruthinate(III)

• [(CO)5Ir(SCN)]-
Pentacarbonylthiocyanato(S)iridate(II).
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For Bridging ligands complexes.

• The prefix µ is used for designating a ligand which

acts as a bridging ligand.
• For two bridging groups of the same kind, di- is
used.

• The bridging ligand is listed in order with the other

ligands separated by a hyphen for unsymmetrical
compounds.
• Symmetrical compounds may be named more
compactly by placing the bridging group first.
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6/4/2020 39
 Qn: Name the following complex:
mer-[Ru{(C2H5)3P}3H3]

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 Isomerism

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 •Isomers are those compounds which have the same
chemical formula but different structural
arrangements of their atoms.

•Different arrangement of atoms due to their

different structures are responsible for their
different physical or chemical properties.

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 1. Stereoisomerism: Stereoisomers have the same
chemical formula and chemical bonds but they
have different special arrangements.

They are further classified as follows:

i. Geometrical isomerism
• It arises in heteroleptic coordination complexes
due to different possible geometric arrangements
of the ligands.

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 •When similar ligands are adjacent to each other, they
form cis isomer and when they are
opposite to each other a trans isomer is formed.

•Geometrical isomerism is very common in complexes

with coordination number 4 and 6.

•For example, platinum ammine complexes are

geometrical isomers, as described below:

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(A) Square Planar Complexes

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 (B) Octrahedral Complexes

(i) Cis – Trans isomers

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(ii) facial (fac) and meridional (mer) isomers

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ii. Optical isomerism
• It arises due to absence of elements of symmetry
(plane of symmetry or axis of symmetry) in the
complex.

.
• Optical isomerism is common in octahedral
complexes involving didentate ligands

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In a coordination compound of the type [CoCl2(en)2]2+
only the cis-isomer shows optical activity

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2. Structural Isomerism

• Besides stereoisomers, the coordination compounds

may show other types of isomers called structural
isomers.

• Have the same molecular formula but different

structural arrangement of atoms or groups of atoms
around central atom or ion.

• Some important ones are mentioned here under

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i. Linkage isomerism
• It arises in the coordination compounds containing
ambidentate ligands.
• An ambidentate ligand can link with the metal
atom/ion in two different ways.
• So two types of structures are formed, called linkage
isomers.

• For example, in the complex [Co(NH3)(NO2)]Cl2, nitrite

ligand is bound to the metal in two different ways a
red form, in which the nitrite ligand is bound through
oxygen (–ONO), and as the yellow form, in which the
nitrite ligand is bound through nitrogen (–NO2).

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 ii. Ligand isomers
• These arise due to the presence of a ligand in its
isomeric forms.

•E.g 1,2-diaminopropane and 1,3-diaminopropane

complexes, or o-, m-, and p-toluidine isomeric
complexes with metal ions or

•Any other similar category of ligands in which

isomerism is already a property of the ligand.

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 iii. Ionization isomers
• These differ in the nature of the ions produced in
solution by the ionization of the metal complex,

• e.g. [Co(NH3)5SO4)]+Br- (red)

[Co(NH3)5Br)]2+SO42- (violet); or

• [Pt(NH3)3I]+Cl- and [Pt(NH3)3Cl]+I-

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iv. Solvate isomers
• These are special cases of ionization isomers which
involve solvent molecules.

• If water is the solvent, hydrate isomers result, the best

known example is the chromium chloride hydrates:
Violet [Cr(H2O)6]Cl3,
Grey green [Cr(H2O)5Cl]Cl2.H2O and
Green [Cr(H2O)4Cl2]Cl.2H2O
which precipitates 3, 2 and 1 mole of chloride ions
respectively, on dissolution with silver nitrate solution.

• Others are [CoCl(en)2(H2O)]Cl2 & [CoCl2(en)2]Cl. H2O

[CoCl(NH3)4(H2O)]Cl2 & [CoCl2(NH3)4(H2O)]Cl. H2O
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 v. Coordinate isomers
• The isomers consist of complex cations and anions
in which the ligands are bound to different metals
in each isomer (due to interchange of one ligand
or more from cation to anion).

Examples include;
[Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6] or

[Cu(NH3)4][PtCl4] and [Pt(NH3)4][CuCl4].

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vi. Coordination position isomers
• Occurs when the complex has the same metal in two
different oxidation states as the cations and anions.

H H
O O

[(NH3)4Co 2+
Co(NH3)2Cl2] and [Cl(NH3)3Co Co(NH3)3Cl]2+

O O
H H

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vii. Polymerization isomers
• Complexes having the same empirical formula but
different molecular formula e.g.

[Co(NH3)4(NO2)2] [Co(NH3)2(NO2)4]
[Co(NH3)6][Co(NO2)6] and
[Co(NH3)5(NO2)][Co(NH3)(NO2)5],

[Co(NH3)6][Co(NH3)2(NO2)4]3,
[Co(NH3)4(NO2)2]3 [Co(NO2)6] and
[Co(NH3)5(NO2)]3 [Co(NO2)6]2
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