AX₃E₂ Molecules: BrF₃

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

Once again, we have a compound that is an exception to the octet rule.

2. There are five groups around the central atom, three bonding pairs and two lone pairs. We again direct the groups toward the vertices of a trigonal bipyramid.

3. With three bonding pairs and two lone pairs, the structural designation is AX₃E₂ with a total of five electron pairs. Because the axial and equatorial positions are not equivalent, we must decide how to arrange the groups to minimize repulsions. If we place both lone pairs in the axial positions, we have six LP–BP repulsions at 90°. If both are in the equatorial positions, we have four LP–BP repulsions at 90°. If one lone pair is axial and the other equatorial, we have one LP–LP repulsion at 90° and three LP–BP repulsions at 90°:

Structure (c) can be eliminated because it has a LP–LP interaction at 90°. Structure (b), with fewer LP–BP repulsions at 90° than (a), is lower in energy. However, we predict a deviation in bond angles because of the presence of the two lone pairs of electrons.

4. The three nuclei in BrF₃ determine its molecular structure, which is described as T shaped. This is essentially a trigonal bipyramid that is missing two equatorial vertices. The F_axial–Br–F_axial angle is 172°, less than 180° because of LP–BP repulsions.

Because lone pairs occupy more space around the central atom than bonding pairs, electrostatic repulsions are more important for lone pairs than for bonding pairs.