Hypervalent Molecules

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Two Lewis structures are shown. The left shows a phosphorus atom single bonded to five chlorine atoms, each with three lone pairs of electrons. The right shows a sulfur atom single bonded to six fluorine atoms, each with three lone pairs of electrons.
Figure 1. In PCl5, the central atom phosphorus shares five pairs of electrons. In SF6, sulfur shares six pairs of electrons. Source: OpenStax Chemistry 2e

Hypervalent Molecules (OpenStax Chemistry 2e)

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. Figure 1 shows the Lewis structures for two hypervalent molecules, PCl5 and SF6.

In some hypervalent molecules, such as IF5 and XeF4, some of the electrons in the outer shell of the central atom are lone pairs:Two Lewis structures are shown. The left shows an iodine atom with one lone pair single bonded to five fluorine atoms, each with three lone pairs of electrons. The right diagram shows a xenon atom with two lone pairs of electrons single bonded to four fluorine atoms, each with three lone pairs of electrons.

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.

Related Topic: Odd-Electron Molecules

Source:

Flowers, P., Theopold, K., Langley, R., & Robinson, W. R. (2019, February 14). Chemistry 2e. Houston, Texas: OpenStax. Access for free at: https://openstax.org/books/chemistry-2e

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