Chemistry - What is Bent's rule?

Solution 1:

That's a good, concise statement of Bent's rule. Of course we could have just as correctly said that p character tends to concentrate in orbitals directed at electronegative elements. We'll use this latter phrasing when we examine methyl fluoride below. But first, let's expand on the definition a bit so that it is clear to all.

Bent's rule speaks to the hybridization of the central atom ($\ce{A}$) in the molecule $\ce{X-A-Y}$.

$\ce{A}$ provides hybridized atomic orbitals that form $\ce{A}$'s part of its bond to $\ce{X}$ and to $\ce{Y}$. Bent's rule says that as we change the electronegativity of $\ce{X}$ and \ or $\ce{Y}$, $\ce{A}$ will tend to rehybridize its orbitals such that more s character will placed in those orbitals directed towards the more electropositive substituent.

Let's examine how Bent's rule might be applied to your example of methyl fluoride. In the $\ce{C-F}$ bond, the carbon hybrid orbital is directed towards the electronegative fluorine. Bent's rule suggests that this carbon hybrid orbital will be richer in p character than we might otherwise have suspected. Instead of the carbon hybrid orbital used in this bond being $\ce{sp^3}$ hybridized it will tend to have more p character and therefore move towards $\ce{sp^4}$ hybridization.

Why is this? s orbitals are lower in energy than p orbitals. Therefore electrons are more stable (lower energy) when they are in orbitals with more s character. The two electrons in the $\ce{C-F}$ bond will spend more time around the electronegative fluorine and less time around carbon. If that's the case (and it is), why "waste" precious, low-energy, s orbital character in a carbon hybrid orbital that doesn't have much electron density to stabilize. Instead, save that s character for use in carbon hybrid orbitals that do have more electron density around carbon (like the $\ce{C-H}$ bonds). So as a consequence of Bent's rule, we would expect more p character in the carbon hybrid orbital used to form the $\ce{C-F}$ bond, and more s-character in the carbon hybrid orbitals used to form the $\ce{C-H}$ bonds.

The physically observable result of all this is that we would expect an $\ce{H-C-H}$ angle larger than the tetrahedral angle of 109.5° (reflective of more s character) and an $\ce{H-C-F}$ angle slightly smaller than 109.5° (reflective of more p character). In terms of bond lengths, we would expect a shortening of the $\ce{C-H}$ bond (more s character) and a lengthening of the $\ce{C-F}$ bond (more p character).

Solution 2:

Have you read the Wikipedia article to Bent's rule (especially the Justification paragraph). I think it explains the things rather well. In the example of $\ce{H3CF}$ the $\ce{H}$ is more electropositive than $\ce{C}$ and the $\ce{F}$ is more electronegative than $\ce{C}$. So, using the assumption that like in $\ce{CH4}$ the $\ce{C}$ atom is $\mathrm{sp}^3$ hybridized as a starting point, Bent's rule tells us that the $\ce{C}$-orbitals that are used to form bonds between $\ce{C}$ and $\ce{H}$ will not be "pure" $\mathrm{sp}^3$ orbitals but will contain a higher $\mathrm{s}$ character whereas the $\ce{C}$-orbital that is used to form the bond between $\ce{C}$ and $\ce{F}$ will contain a higher $\mathrm{p}$ character than a "pure" $\mathrm{sp}^3$ orbital. As for bond angles: the consequences of Bent's rule for the bond angles are also explained rather well in the Wikipedia article.