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Effective Atomic Number (EAN) rule

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 Effective Atomic Number (EAN) Rule
1. The number of secondary valences in the Werner theory is called the
coordination number of the central metal in the complex. This is the number
of ligand atoms bonded to the central metal ion. Each ligand donates an
electron pair to the metal ion, thus forming a coordinate bond.
2. Transition metals form coordination compounds very readily because they
have vacant d orbitals which can accommodate these electron pairs. The
electronic arrangement of the noble gases is known to be very stable.
3. Sidgwick, with his effective atomic number rule, suggested that electron pairs
from ligands were added until the central metal was surrounded by the same
number of electrons as the next noble gas.
4. The total number of electrons which the central metal ion appears to
possess in the complex including those gained by it in bonding is called the
effective atomic number of the central metal ion.
5. According, the effective atomic number in a complex should be equal to 36
(electrons in Krypton), 54 (electrons in xenon) or 86 (electrons in radon).

EAN = [Atomic number - electrons lost in ion formation + (electrons gained

by coordination)]

Calculation of electrons lost in ion formation-

[Fe(CN)6]-4 , the oxidation number of Fe is XFe+6XCN= -4
XFe+ 6(-1) = -4
XFe = +2 (two electrons lost in ion formation)
[Co(NH3)6]3+
XCo+6XNH3 = +3
XCo+ 6(0) = +3 (Three electrons lost in ion formation)
XCo = +3
[Ni(CO)4]
XNi + XCO = 0
XNi + (0)4 = 0 (No electrons lost in ion formation)

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EAN Rule examples
Consider potassiumhexacyanoferrate (II) K4[Fe(CN)6] (formerly called potassium
ferrocyanide). An iron atom has 26 electrons, and so the central metal ion Fe2+
has 24 electrons.
EAN = [Atomic number - electrons lost in ion formation + (electrons gained by
coordination)]
EAN = [26 – 2 + (12)] = 36
Note- Each ligand donates two electrons here 6 cyano groups donates 12
electrons)
The next noble gas Kr has 36 electrons. Thus the addition of six electron pairs
from six CN- ligands adds 12 electrons, thus raising the effective atomic number
(EAN) of Fe2+ in the complex [Fe(CN)6)4- to 36. [24 + (6 x 2) = 36)

Effective atomic numbers of some metals in complexes

Atom Atomic Complex Electrons Electrons EAN
number lost in ion gained by
formation coordination
Cr 24 [Cr(CO)6] 0 (6X2) = 12 [24+(6X2)] =36 (Kr)
Fe 26 [Fe(CN)6]4- 2 (6X2) = 12 [24+(6X2)] =36 (Kr)
Fe 26 [Fe(CO)5] 0 (5X2) = 10 [26+(5X2)] =36 (Kr)
Co 27 [Co(NH3)6]3+ 3 (6X2) = 12 [24+(6X2)] =36 (Kr)
Ni 28 [Ni(CO)4] 0 (4X2) = 8 [28+(4X2)] =36 (Kr)
Cu 29 [Cu(CN)4]3- 1 (4X2) = 8 [28+(4X2)] =36 (Kr)
Pd 46 [Pd(NH3)6]4+ 4 (6X2) = 12 [42+(6X2)] =54 (Xe)
Pt 78 [PtCl6]2- 4 (6X2) = 12 [74+(6X2)] =86 (Xe)
Fe 26 [Fe(CN)6]3- 3 (6X2) = 12 [23+(6X2)] = 35
Ni 28 [Ni(NH3)6]2+ 2 (6X2) = 12 [26+(6X2)] = 38
Pd 46 [PdCl4]2- 2 (4X2) = 8 [44+(4X2)] = 52
Pt 78 [Pt(NH3)4]2+ 2 (4X2) = 8 [76+(4X2)] = 84

6) The EAN rule correctly predicts the number of ligands in many complexes.
There are, however, a significant number of exceptions where the EAN is not
quite that of a noble gas. If the original metal ion has an odd number of
electrons, for example, the adding of electron pairs cannot result in a noble gas
structure.

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7) The tendency to attain a noble gas configuration is a significant factor but not
a necessary condition for complex formation. It is also necessary to produce a
symmetrical structure involved. (tetrahedral, square planar, octahedral)
irrespective of the number of electrons involved.
Ref-
Principles of Inorganic Chemistry – Late B. R. Puri, L.S Sharma, K.C. Kalia
Concise of Inorganic Chemistry – J.D Lee

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