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Chemistry LibreTexts

Exceptions to the Octet Rule

There are three general ways in which the octet rule breaks down:

  1. Molecules with an odd number of electrons
  2. Molecules in which an atom has less than an octet
  3. Molecules in which an atom has more than an octet

Odd number of electrons

Draw the Lewis structure for the molecule nitrous oxide (NO):

1. Total electrons: 6+5=11

2. Bonding structure:

3. Octet on "outer" element:

4. Remainder of electrons (11-8 = 3) on "central" atom:

5. There are currently 5 valence electrons around the nitrogen. A double bond would place 7 around the nitrogen, and a triple bond would place 9 around the nitrogen.

We appear unable to get an octet around each atom

Less than an Octet

This is most often encountered with elements of Boron and Beryllium.

Draw the Lewis structure for boron trifluoride (BF3):

1. Add electrons (3*7) + 3 = 24

2. Draw connectivities:

3. Add octets to outer atoms:

4. Add extra electrons (24-24=0) to central atom:

5. Does central electron have octet?

  • NO. It has 6 electrons
  • Add a multiple bond (double bond) to see if central atom can achieve an octet:

6. The central Boron now has an octet (there would be three resonance Lewis structures)

However...

  • In this structure with a double bond the fluorine atom is sharing extra electrons with the boron.
  • The fluorine would have a '+' partial charge, and the boron a '-' partial charge, this is inconsistent with the electronegativities of fluorine and boron.
  • Thus, the structure of BF3, with single bonds, and 6 valence electrons around the central boron is the most likely structure

BF3 reacts strongly with compounds which have an unshared pair of electrons which can be used to form a bond with the boron:

 

More than an octet

This is most common example of exceptions to the octet rule.

PCl5 is a legitimate compound, whereas NCl5 is not.

Expanded valence shells are observed only for elements in period 3 (i.e. n=3) and beyond

  • The 'octet' rule is based upon available ns and np orbitals for valence electrons (2 electrons in the s orbitals, and 6 in the p orbitals)
  • Beginning with the n=3 principal quantum number, the d orbitals become available (l=2)

The orbital diagram for the valence shell of phosphorous is:

Third period elements occasionally exceed the octet rule by using their empty d orbitals to accommodate additional electrons

Size is also an important consideration:

  • The larger the central atom, the larger the number of electrons which can surround it
  • Expanded valence shells occur most often when the central atom is bonded to small electronegative atoms, such as F, Cl and O.

Draw the Lewis structure for ICl4-

1. Count up the valence electrons: 7+(4*7)+1 = 36 electrons

2. Draw the connectivities:

3. Add octet of electrons to outer atoms:

4. Add extra electrons (36-32=4) to central atom:

5. The ICl4- ion thus has 12 valence electrons around the central Iodine (in the 5d orbitals)