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Exceptions to the Octet Rule

Exceptions to the Octet Rule

Many covalent molecules have central atoms that do not have eight electrons in their Lewis structures. These molecules fall into three categories:

  • Odd-electron molecules have an odd number of valence electrons, and therefore have an unpaired electron.
  • Electron-deficient molecules have a central atom that has fewer electrons than needed for a noble gas configuration.
  • Hypervalent molecules have a central atom that has more electrons than needed for a noble gas configuration.

Odd-electron Molecules

We call molecules that contain an odd number of electrons free radicals. Nitric oxide, NO, is an example of an odd-electron molecule; it is produced in internal combustion engines when oxygen and nitrogen react at high temperatures.

To draw the Lewis structure for an odd-electron molecule like NO, we follow the same five steps we would for other molecules, but with a few minor changes:

  1. Determine the total number of valence (outer shell) electrons. The sum of the valence electrons is 5 (from N) + 6 (from O) = 11. The odd number immediately tells us that we have a free radical, so we know that not every atom can have eight electrons in its valence shell.
  2. Draw a skeleton structure of the molecule. We can easily draw a skeleton with an N–O single bond:
    N–O
  3. Distribute the remaining electrons as lone pairs on the terminal atoms. In this case, there is no central atom, so we distribute the electrons around both atoms. We give eight electrons to the more electronegative atom in these situations; thus oxygen has the filled valence shell:
    Exceptions to the Octet Rule
  4. Place all remaining electrons on the central atom. Since there are no remaining electrons, this step does not apply.
  5. Rearrange the electrons to make multiple bonds with the central atom in order to obtain octets wherever possible. We know that an odd-electron molecule cannot have an octet for every atom, but we want to get each atom as close to an octet as possible. In this case, nitrogen has only five electrons around it. To move closer to an octet for nitrogen, we take one of the lone pairs from oxygen and use it to form a NO double bond. (We cannot take another lone pair of electrons on oxygen and form a triple bond because nitrogen would then have nine electrons:)
    Exceptions to the Octet Rule

Electron-deficient Molecules

We will also encounter a few molecules that contain central atoms that do not have a filled valence shell. Generally, these are molecules with central atoms from groups 2 and 13, outer atoms that are hydrogen, or other atoms that do not form multiple bonds. For example, in the Lewis structures of beryllium dihydride, BeH2, and boron trifluoride, BF3, the beryllium and boron atoms each have only four and six electrons, respectively. It is possible to draw a structure with a double bond between a boron atom and a fluorine atom in BF3, satisfying the octet rule, but experimental evidence indicates the bond lengths are closer to that expected for B–F single bonds. This suggests the best Lewis structure has three B–F single bonds and an electron deficient boron. The reactivity of the compound is also consistent with an electron deficient boron. However, the B–F bonds are slightly shorter than what is actually expected for B–F single bonds, indicating that some double bond character is found in the actual molecule.

Exceptions to the Octet Rule

An atom like the boron atom in BF3, which does not have eight electrons, is very reactive. It readily combines with a molecule containing an atom with a lone pair of electrons. For example, NH3 reacts with BF3 because the lone pair on nitrogen can be shared with the boron atom:

Exceptions to the Octet Rule

Hypervalent Molecules

Elements in the second period of the periodic table (n = 2) can accommodate only eight electrons in their valence shell orbitals because they have only four valence orbitals (one 2s and three 2p orbitals). Elements in the third and higher periods (n ≥ 3) have more than four valence orbitals and can share more than four pairs of electrons with other atoms because they have empty d orbitals in the same shell. Molecules formed from these elements are sometimes called hypervalent molecules. The figure below shows the Lewis structures for two hypervalent molecules, PCl5 and SF6.

Exceptions to the Octet Rule

In PCl5, the central atom phosphorus shares five pairs of electrons. In SF6, sulfur shares six pairs of electrons.

In some hypervalent molecules, such as IF5 and XeF4, some of the electrons in the outer shell of the central atom are lone pairs:

Exceptions to the Octet Rule

When we write the Lewis structures for these molecules, we find that we have electrons left over after filling the valence shells of the outer atoms with eight electrons. These additional electrons must be assigned to the central atom.

Example: Writing Lewis Structures: Octet Rule Violations

Xenon is a noble gas, but it forms a number of stable compounds. We examined XeF4 earlier. What are the Lewis structures of XeF2 and XeF6?

Solution

We can draw the Lewis structure of any covalent molecule by following the six steps discussed earlier. In this case, we can condense the last few steps, since not all of them apply.

  1. Calculate the number of valence electrons:
    XeF2: 8 + (2 \(×\) 7) = 22
    XeF6: 8 + (6 \(×\) 7) = 50
  2. Draw a skeleton joining the atoms by single bonds. Xenon will be the central atom because fluorine cannot be a central atom:
    Exceptions to the Octet Rule
  3. Distribute the remaining electrons.
    XeF2: We place three lone pairs of electrons around each F atom, accounting for 12 electrons and giving each F atom 8 electrons. Thus, six electrons (three lone pairs) remain. These lone pairs must be placed on the Xe atom. This is acceptable because Xe atoms have empty valence shell d orbitals and can accommodate more than eight electrons. The Lewis structure of XeF2 shows two bonding pairs and three lone pairs of electrons around the Xe atom:
    Exceptions to the Octet Rule
    XeF6: We place three lone pairs of electrons around each F atom, accounting for 36 electrons. Two electrons remain, and this lone pair is placed on the Xe atom:
    Exceptions to the Octet Rule

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