Question #2f3a0

1 Answer
Feb 26, 2017

It's the other way around. The trimethyl compound is nonpolar. Here's why.

Explanation:

Shapes

Both molecules have five ligands about the "P"P atom, so they have trigonal pyramidal shapes.

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Orbitals

We say that the "P"P atom is "sp"^3"d"sp3d hybridized.

However, the equatorial and axial orbitals form two different sets.

We can view the equatorial set as being formed from one "s"s, one "p"_xpx, and one "p"_ypy orbital (33 % "s"s character per orbital).

The axial set is formed from one "p"_zpz and one "d"d orbital (0 % "s"s character per orbital).

Bent's rule

Bent's rule states that atomic "s"s character concentrates in orbitals directed toward electropositive substituents.

The corollary is that orbitals with less "s"s character are directed toward electronegative substituents.

Structures

"CF"_3CF3 groups are more electronegative than "CH"_3CH3 groups.

Hence, they will preferentially occupy the axial positions.

Structures
(Adapted from hope.simons-rock.edu)

In the trimethyl compound (2), the "CF"_3CF3 groups are both axial, and all bond dipoles cancel. The molecule is nonpolar.

In the dimethyl compound (1), one of the "CF"_3CF3 groups must occupy an equatorial position, and the equatorial bond dipoles no longer cancel. The molecule is polar.