AX₄E Molecules: SF₄

1. The sulfur atom has six valence electrons and each fluorine has seven valence electrons, so the Lewis electron structure is

With an expanded valence, this species is an exception to the octet rule.

2. There are five groups around sulfur, four bonding pairs and one lone pair. With five electron groups, the lowest energy arrangement is a trigonal bipyramid.

3. We designate SF₄ as AX₄E; it has a total of five electron pairs. However, because the axial and equatorial positions are not chemically equivalent, where do we place the lone pair? If we place the lone pair in the axial position, we have three LP–BP repulsions at 90°. If we place it in the equatorial position, we have two 90° LP–BP repulsions at 90°. With fewer 90° LP–BP repulsions, we can predict that the structure with the lone pair of electrons in the equatorial position is more stable than the one with the lone pair in the axial position. We also expect a deviation from ideal geometry because a lone pair of electrons occupies more space than a bonding pair.

Figure 1.1 : Illustration of the Area Shared by Two Electron Pairs versus the Angle between Them

At 90°, the two electron pairs share a relatively large region of space, which leads to strong repulsive electron–electron interactions.

4. With four nuclei and one lone pair of electrons, the molecular structure is based on a trigonal bipyramid with a missing equatorial vertex; it is described as a seesaw. The F_axial–S–F_axial angle is 173° rather than 180° because of the lone pair of electrons in the equatorial plane.