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The familiar VSEPR (Valence Shell Electron Pair Repulsion) approach to molecular structure was developed by Ronald Gillespie. The basic idea is that lone pairs of electrons occupy space around a central atom in much the same way as do atoms that are bonded to the central atom. The lone pairs and bonded atoms then assume that geometry that minimizes electrostatic repulsion

between them.

Ronald Gillespie.

electron domains and molecular geometry
Electron domains and molecular geometry:

observed geometry is

that where the electron

domains are as far apart

as possible

each lone pair of electrons

plus each atom bonded to the

central atom constitute an

electron ‘domain’

lone pair

of electrons





Lewis dot diagram

of ammonia


trigonal pyramidal

(derived from tetrahedral geometry)

using vsepr

In order to use VSEPR to predict molecular structure:

  • Draw up Lewis dot diagram for the molecule or ion. The first atom (e.g. Br in BrF5) is always the central atom. Place the other atoms around the central atom.

If these are single bonds, contribute one electron per attached atom. Then add the valence electrons for the central atom = 7 for Br.

2) Work out number of electron domains = valence electron pairs (‘n’) plus attached atoms on central atom. For BrF5 n = 6.

3) Relate n to the type of structure predicted for that value of n. n = 6 = octahedral.

4) Place lone pairs in expected positions, maximizing separation of lone pairs. For BrF5, there is one lone pair, so mol. structure = square pyramidal.

place 5 F

atoms around

central Br

red = 7 valence

electrons for Br

the structure of brf 5 from vsepr
The structure of BrF5 from VSEPR:

Lewis dot diagram

parent structure

molecular structure =

square pyramidal

lone pair

n = 6, parent structure

= octahedral, but one site

occupied by a lone pair

molecular or final

structure – disregard

the lone pair

n = 6 from five

attached atoms

plus one electron


parent shapes for ex n molecules n 2 5
Parent shapes for EXn molecules (n = 2-5)

Formula n shapeshapes of structures

EX2 2 linear

EX3 3 trigonal planar

EX4 4 tetrahedral

EX5 5 trigonal


parent shapes for ex n molecules n 6 8
Parent shapes for EXn molecules (n = 6-8)

Formula n shapeshapes of structures

EX6 6 octahedral

EX7 7 pentagonal


EX8 8 square


a series of derivatives of the ex 4 geometry all with n 4 but with increasing numbers of lone pairs
A series of derivatives of the EX4 geometry (all with n = 4) but with increasing numbers of lone pairs:



Methane ammonia water hydrogen fluoride

Tetrahedral trigonal pyramid bent linear diatomic

structures derived from trigonal geometry n 3
Structures derived from trigonal geometry (n = 3):

lone pair

trigonal planar bent

boron trifluoride nitrite anion, NO2-

trigonal planar bent

ozone a bent molecule
Ozone – a bent molecule:

The structure of the O3 (ozone) molecule can be predicted using VSEPR. First draw up the Lewis dot diagram:

For the valence shell of the

central oxygen atom n = 3,

so parent geometry =

trigonal. The final structure is thus two-coordinate bent, as seen for the ozone molecule below:

Note that two pairs

of e’s still count as

only one electron

domain = one

attached O-atom

Central atom

(red valence


Structure of the ozone

molecule (oxygens =

red atoms)



Negative charge adds a valence electron to iodine.


Note: The way the number of valence electrons (= 12) on the iodine is

derived is from the seven valence electrons for iodine (group 7

in the periodic table), plus one each from the F-atoms, and one from

the negative charge on the complex.

example chlorine trifluoride
Example: Chlorine trifluoride

NOTE: in structures derived from a TBP parent structure, the lone pairs

always lie in the plane, as seen here for the T-shaped structure of ClF3.

the structure of if 5 c 6 h 5 note an aliphatic or aromatic group is equivalent to an f
The structure of [IF5(C6H5)]-:Note: an aliphatic or aromatic group is equivalent to an F.

phenyl group



S.Hoyer, K.Seppelt (2004) J. Fluorine Chem. ,125, 989

diphenyl acetato iodine v oxide

carbon atoms

from phenyls




phenyl group

two pairs

of electrons

= double bond

oxygen from

acetato group


The structure of bis(pentafluorophenyl)xenon. VSEPR explains this type of structure, which is linear like XeF2. (explain the latter in terms of VSEPR)



phenyl group

H.Bock, D.Hinz-Hubner, U.Ruschewitz, D.Naumann

(2002) Angew.Chem.,Int.Ed. , 41, 448

the i c 6 h 5 2 cation
The [I(C6H5)2]+ cation:


phenyl group

bis trifluoroacetato phenyl iodine iii




phenyl group

the effect of lone pairs on bond angles
The effect of lone pairs on bond angles:

In VSEPR the lone pairs appear to occupy more space than electron pairs in bonds, with the result that bond angles are compressed away from the lone pairs. For example, in structures derived from tetrahedral parent geometry, such as water or ammonia, the H-O-H and H-N-H angles are compressed to be less than the 109.5º expected for a regular tetrahedron:

lone pairs



effects of lone pairs on bond angles in clf 3 and clf 5
Effects of lone pairs on bond angles in ClF3 and ClF5.



chlorine trifuoride chlorine pentafluoride