Formal Charge

Formal charge is a way for us to keep track of electrons. In organic chemistry, you will not only need to calculate formal charges but also understand what they mean and how to use them. You will use formal charges to understand structures, intermediates, and reaction mechanisms.

Calculating formal charge

Let us go over the textbook definition first! The formal charge is usually defined as follows;

You simply subtract the number of lone pair electrons and 1/2 the bonding electrons (or simply the number of bonds) from the number of valence electrons. Let's try it for ourselves.

Practice Problem

What is the formal charge on the carbon atoms in the following structure?

How many valence electrons does carbon have? Well, you need to have a periodic table and count from the left until you hit the atom of interest. So for C is Li one, Berylium two, boron three, and finally carbon 4. Thus carbon has 4 valence electrons.

How many lone pairs does the C in the above structure have? zero (0)

What is half the number of bonding electrons? 6/2=3 or just the number of bonds.

Formal Charge (Carbon atom) = 4 - 0 - 3 = +1

We would write the + next to the carbon as follows;

What does it really mean?

First of all, there is no reason to memorize the above equation if you realize that formal charge is simply the number of electrons an atom wants to have minus the number of electrons it actually has (or owns). You'll notice that we only subtract half the bonding electrons. Since these are covalent bonds the electrons are shared and the carbon only owns one of the two electrons in each bond, while the H atom owns the other electron.

Limitations of Formal Charge

Calculate the formal charge on the nitrogen atom in the following structure.

From the periodic table you see that nitrogen has 5 valence electrons (i.e. it wants to have 5 electrons around it). The nitrogen in the structure above has only 4 electrons about it that it owns, so the formal charge is 5 - 4 = +1 and we would write the structure as follows. This is called an ammonium ion.

Let us compare the methyl carbocation and ammonium ion to gain an appreciation of what's going on.

Think about why each structure has a positive formal charge. In the case of the ammonium ion, it is because the nitrogen atom is sharing its lone pair electrons with hydrogen (proton). On the other hand, the methyl cation just does not have enough electrons. Because of this, they behave differently. For example, something that likes a positive charge (i.e. a nucleophile) will attack the carbon atom of the methyl cation. However, a nucleophile will never attack the positive nitrogen atom.

Common patterns

While it is important to be able to calculate the formal charge under any circumstances, it is also helpful to notice when atoms, which are common to organic chemistry (such as carbon, nitrogen, and oxygen), would be expected to have a formal charge. For instance, you may have noticed that neutral carbon always makes four bonds. Similarly neutral nitrogen makes three bonds and neutral oxygen makes two bonds. If these atoms make a different number of bonds other than the numbers just listed, they will have a formal charge. If you train your brain to easily recognize these patterns, then writing structures for intermediates and reaction mechanisms will be easier.

Your Turn

Action

Complete the following table, which summarizes some of these patterns by dragging the number of bonds (1,2,3 or 4) on to the appropriate drop zones to indicate the number of bonds for that atom with the corresponding charge. For example, you would drag a 4 onto the carbon row under 0 charge, since a neutral carbon has 4 bonds.