Lecture 2 The Effective Atomic Number

LECTURE 2: 18 ELECTRON RULE OR THE
EFFECTIVE ATOMIC NUMBER (EAN

RULE)
PROF LYDIA W. NJENGA

DEPARTMENT OF CHEMISTRY
UON
EFFECTIVE ATOMIC NUMBER (EAN) OR 18e RULE
The EAN OR 18e Rule= The sum of the electrons on the metal
[nsx (n-1)d ynpz ] or the valence electron: [nd + (n+1)s + (n+1)p] plus
the electrons donated from the ligands was called the effective atomic
number. (tendency to attain noble gas structure)
• EAN = 18 (Ar), 36 (Kr), 54 (Xe), 86 Rn) Then they obey the EAN rule
• This rule is mostly obeyed by the organometallic compounds especially those of

carbonyl (CO) and nitrosyl (NO) ligands
EAN : K4[Fe(CN)6
• Method A • Method B
• Using the valence electron of the metal • Using the total No of metal electrons
• Fe [Ar] 3d6 4s2 Total Valence electrons • Fe [Ar] 3d6 4s2 Total electrons =26
=8 • ON =+2
• ON =+2 • Therefore, Fe contribute 26-2=24e)
• Therefore, Fe contribute (8-2) = 6 e • Ligand 6CN : 2x6 = 12
• Ligand 6CN : 2x6 = 12 • Total e =24 + 12 = 36e
• Total e = 6 + 12 = 18e • [Krypton]- obey
• [Argon]= obey
EAN Cont’d
• Work out the EAN rule of Mo(CO)6, Re2(CO)12.
1. Assign the metal a positive oxidation Number equal to the sum

of negative charges on the ligand and the total charge of
complex count the Number of electrons it contributes. Work
out the oxidation state of the metal.
2. Each linearly (terminal) bonded CO contributes 2 electrons.
3. Each metal in M-M bond contributes 1 electron.
4. Each Bridging CO contribute 1 e-

EXAMPLES: Mo(CO)6 Oh (octahedron)
• Mo = 4d5 5s1
• Valence electron =6
• charge on Mo = 0
• Total electron = electrons of
Mo(o) + electrons of 6 CO
• Mo(0) = 6
• 6 ligands = 6x2 = 12
• Total = 18e- - obey EAN rule
Mn(CO)5CH3.
• Mn [Ar}3d54s2
• Valence e for Mn = 7
• 5 Co gps each donates 2 electrons = 2x5 =10
• 1 methyl group donate 1 e =1
• Total number of electrons: 7 + 10 + 1 = 18e

M-M bond calculation
• Method A: The whole molecule Method B: Using only one M
i) Determine the valence e of the center:
metal i.e Yx 2= 2Ye i) Determine the valence e of the
ii) Number of M-M bond: each metal =Y
m-m bond contributes 2e (for ii) Determine the M—m bonds. Each
1M-M) metal bond will contribute 1 e to that
iii) Determine the total number of center
the ligands n; each ligands iii) Determine total number of
contribute 2e, (2ne) ligands nx2 = 2ne
• Total e = 2Y + 2 (M-M) + 2n • Total e- = Y + 1 (for 1M_M) + 2n

Re2(CO)10 (D4h)
• Re =5d54s2
• Valence electrons = 7
• Re(0) + 5 x CO + 1 Re-Re bond:
• Re(o) = 7
• Re-Re =1
• 5CO = 10 (terminal CO)
• Total = 18e : obeys
• The whole molecule
• 2 Re = 14
• 10 Co = 20
• 1Re-Re = 2
Ref: Wikimedia commons
• Total = 14 + 20 + 2 = 36e
Fe2(CO)9
• bridged CO’s, each CO
contributes 1e- to the metal
• Fe(O) =[Ar]3d64s2
• Valence electron = 8e
• 3Terminal CO = 6e
• 3bridged CO = 3e
• 1m-m =1e
• Total = 18e 0bey
Ref: Sematic scholar

EAN cont’d
• Fe[Ar]3d64s2
• Bridging CO:
•
• Fe0 +3 terminal CO + 2µCO (Bridged) +
2Fe-Fe bond
• = 8 + (3x2) + (2x1) + (2x1)
• Total=18 electrons
Fe3(CO)12
Work out the EAN for Rh2(CO) 4Cl2 ,Al2(CH3)6 and Ir4(CO)12
Some common multihaptic ligands.
The term used to describe the participation of multiple atoms simultaneously during
pi coordination is hapticity. η 1 – Monohapto; η 3 – trihapto; η 5 – pentahapto. For
alkene like ethene, it is dihaptic η2 (2 carbons participate), 1,3-butadiene is tetraheptic
η4. In η 5 –cyclopentadienyl 5 carbon atoms participate
Fe(C5H5)2 Ni(C3H5)2
Fe2+: (3d6) = 6e
2 C5H5- = 2(5+1) =12e Ni0 (Ar 3d84s2) = 10e
Total = 18e Ally groups 2C3H5 = 2x3=6e
obey Total = 16e Does not
obey
Ref: Wikimedia commons

• Re [Xe] 4f14 5d5 6s2
• Re = +1
• VE for Re = 6
• Total ligands 6 each contributes

2 electrons (2x6) = 12
• Total = 6 + 12 = 18e
H/W
• Calculate the EAN of the following
• (μ-CO)-[ɳ4 -(C4 H4 ) Fe(CO)2]2
• [Cr(ɳ3-C5H 5)(CO) n (CH 3)]

Identification of the unknown metal
[Co(CO)5]z
[M(CO)7]+
• Find the oxidation state of the

• Identify the unknown metal
complex.
• 1. 18 e rule
• Total electrons =18
• Co = [Ar]3d74s2
• 2. Each ligand contribute 2 e +
2x 7 = 14 e • Metal electron =9
• Oxidation state = x
• Each Co contributes 2e ( 2x 5) = 10e
• 18-14 = 4 therefor d4
• 9 + 10 = 19e
• Have lost 1 electron • 18 e rule: 19-18= 1
• Therefor Co is in oxidation state +1
• Metal M= V • Overall charge = +
organometallic ligands and their respective electron contribution
Neutral 2e donors Anionic 2e donors Anionic 4e donors Anionic 6e donors

Cp-
PR3 (phosphines) X- (halide) C3H5- (allyl)
(cyclopentadienyl)
CO (carbonyl) CH3- (methyl) O2- (oxide) O2- (oxide)
alkenes CR3- (alkyl) S2- (sulfide)
alkynes Ph- (phenyl) NR2- (imide)
nitriles H- (hydride) CR22- (alkylidene)
RnE- (silyl, germyl, OR- (alkoxide,
alkoxo, amido etc.) bridging ligand)
SR- (thiolate,
bridging ligand)
NR2- (inorganic
amide, bridging
ligand)
Sturdy questions
• Given the following compounds, determine the number of valency
electrons of the metal and comment whether it obeys the EAN rule
Study questions
• Work out the EAN rule in:
a. Mo(CO)6,
b. Re2(CO)12
c. Co(CO)4-
d. Mn(CO)6+.
e. [V(CO)6]-
f. (η5–C5H5)2Fe
g. [Re(CO)5(PF3)]+
h. [Fe(CO)2(CN)4]2-
i. (Ph3P)2Ir(CO)Cl
j. Fe(CO)2(NO)2
k. Co6(CO)16
l. [Pt((C3H4)2Cl3]

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LECTURE 2: 18 ELECTRON RULE OR THE

EFFECTIVE ATOMIC NUMBER (EAN

PROF LYDIA W. NJENGA

• This rule is mostly obeyed by the organometallic compounds especially those of

• Work out the EAN rule of Mo(CO)6, Re2(CO)12.

1. Assign the metal a positive oxidation Number equal to the sum

2. Each linearly (terminal) bonded CO contributes 2 electrons.

3. Each metal in M-M bond contributes 1 electron.

4. Each Bridging CO contribute 1 e-

• 5 Co gps each donates 2 electrons = 2x5 =10

• 1 methyl group donate 1 e =1

• Total number of electrons: 7 + 10 + 1 = 18e

• Total e = 2Y + 2 (M-M) + 2n • Total e- = Y + 1 (for 1M_M) + 2n

Ref: Sematic scholar

• = 8 + (3x2) + (2x1) + (2x1)

Ref: Wikimedia commons

• Total ligands 6 each contributes

• Calculate the EAN of the following

• (μ-CO)-[ɳ4 -(C4 H4 ) Fe(CO)2]2

• [Cr(ɳ3-C5H 5)(CO) n (CH 3)]

• Find the oxidation state of the

Neutral 2e donors Anionic 2e donors Anionic 4e donors Anionic 6e donors

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