9.12
The octet rule explains chemical bonding in main group compounds by predicting that each atom reaches an 8-electron configuration. However, there are three major exceptions to this rule.
The first exception is odd-electron species. Most molecules and ions have an even number of electrons. However, certain molecules, called radicals, have one or more unpaired electrons. Radicals with an odd number of unpaired electrons cannot achieve octets.
The superoxide anion, a radical with one unpaired electron, has 13 valence electrons. It can be represented by two contributing structures where one oxygen has only seven electrons and thus cannot reach an octet.
The second exception is atoms that form an incomplete octet. For instance, hydrogen, helium, and lithium tend to reach a duet, whereas elements of group 2 and 13, like beryllium and boron, often form molecules with four and six electrons around them, respectively.
Consider aluminum chloride, which has 24 valence electrons. While all chlorine atoms reach the octet, aluminum gets only 6 valence electrons — an incomplete octet.
Although aluminum chloride is stable, it reacts with molecules like ammonia that have an unshared pair of electrons. The nitrogen in ammonia donates its lone pair to aluminum, forming a special bond called a coordinate covalent or dative bond.
The third exception is elements that can accommodate more than 8 valence electrons or an expanded octet. These elements are located in the third row of the periodic table and below.
Elements, such as phosphorus, sulfur, or iodine, have access to d orbitals, allowing them to accommodate more than 8 valence electrons — often up to 12 or 14.
Consider the tetrachloroiodide anion, which has 36 valence electrons. Even after assigning the bonding electron pairs and satisfying the octet for all atoms, 4 valence electrons remain unassigned.
These electrons are placed on the central iodine atom, yielding an expanded octet with 12 electrons. Molecules with more than 8 valence electrons around the central atom are called hypervalent.
Remember, elements from the second row of the periodic table, such as carbon or oxygen, have only s and p orbitals and never form hypervalent compounds because collectively they can only hold up to 8 valence electrons.
Many covalent molecules have central atoms that do not have eight electrons in their Lewis structures. These molecules fall into three categories:
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