16.5 Electron Delocalization, Hybridization, and Geometry

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Let’s see if we can correlate these drawing conventions to a valence bond theory picture of the bonding in a carboxylate group. We know that the carbon must be sp²-hybridized, (the bond angles are close to 120˚, and the molecule is planar), and we will treat both oxygens as being sp²-hybridized as well. Both carbon-oxygen sbonds, then, are formed from the overlap of carbon sp² orbitals and oxygen sp² orbitals.

In addition, the carbon and both oxygens each have an unhybridized 2p_z orbital situated perpendicular to the plane of the sigma bonds. These three 2p_z orbitals are parallel to each other, and can overlap in a side-by-side fashion to form a delocalized pi bond.

Resonance contributor A shows oxygen #1 sharing a pair of electrons with carbon in a pi bond, and oxygen #2 holding a lone pair of electrons in its 2p_z orbital. Resonance contributor B, on the other hand, shows oxygen #2 participating in the pi bond with carbon, and oxygen #1 holding a lone pair in its 2p_z orbital. Overall, the situation is one of three parallel, overlapping 2p_z orbitals sharing four delocalized pi electrons. Because there is one more electron than there are 2p_z orbitals, the system has an overall charge of –1. This is the kind of 3D picture that resonance contributors are used to approximate, and once you get some practice you should be able to quickly visualize overlapping 2p_z orbitals and delocalized pi electrons whenever you see resonance structures being used. In this text, carboxylate groups will usually be drawn showing only one resonance contributor for the sake of simplicity, but you should always keep in mind that the two C-O bonds are equal, and that the negative charge is delocalized to both oxygens.

Organic Chemistry With a Biological Emphasis by Tim Soderberg (University of Minnesota, Morris)