CHEM 109A Drawing Resonance Structures

CLAS

Resonance structures (a.k.a. resonance contributors) are structures drawn to show the possible locations of delocalized electrons. Use a double headed arrow () between structures to indicate that they are resonance contributors, and curved arrows to show how e-s moved. Resonance structures differ from each other ONLY in the location of the e-s and lone pairs (they must have same atoms connected in the same order. If the connectivity or orientation of the atoms changes then the structures are considered isomers which we will discuss in Ch 5). Resonance contributors are representations of what the molecule looks like at a given instance in time. The true molecular structure is a combination or hybrid of the most significant (read stable) resonance contributors. Drawing Resonance Strucutures/Contributors: See also Special Topic V: Drawing Resonance Contributors in Study Guide and Solutions Manual of text. 1. Draw a Lewis structure (be sure to include all lone pairs) 2. Use curved arrows to show how electrons (e-) move: Tail of a curved arrow shows where e- came from (multiple bond or lone pair, never a + charge or empty space). Head of curved arrow shows where e- go to (point between atoms to form a multiple bond or point to an atom usually with a positive charge or fairly electronegative to form lone pair, never into a charge and only very rarely into empty space (EX. Diels-Alder reactions, radical reactions)). Two rules/commandments 1. Do NOT break a single bond. 2. Do NOT exceed an octet for second-row elements (C, N, O, F) can have less than an octet (use formal charge) but NOT more or 12 electrons for a third-row element (P, S, etc).
O R

violates rule 2

violates rule 1 OK For example 1. For each set of drawings below, draw the curved arrow(s) that get from one structure to the next. c.
N + N

a. b.
N+ N

d.

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CHEM 109A Drawing Resonance Structures e.

O O-

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f.

-O O

2. For each of the compounds below, draw all resonance contributors.

O

a.

d.
N OH

b.
O

e. c. Cl Predicting Relative Stability of Resonance Structures/Contributors: Factors that INCREASE Stability Factors that DECREASE Stability complete octets on all atoms incomplete octets no formal charge (FC) separated charges/large FC/ like charges on adjacent atoms more covalent bonds fewer covalent bonds negative FC on more EN atoms negative FC on less EN atoms positive FC on less EN atoms positive FC on more EN atoms Some examples comparing stabilities
O O-

H2 C
H
OC+

N +

N-

H2C

HO

+HO

less stable
O+ CO

least stable
N H3 C N + N-

most stable
+N H3C N + N-

H 2C

H3+ C

N-

less stable

less stable

less stable

The more stable a resonance structure, the lower its energy and the more it contributes to the structure of the hybrid/actual molecule. The hybrid can be thought of as a weighted (based on stability) average of the resonance structures. In general, the more resonance structures you can draw for a particular compound, the more stable that compound this is attributed to Resonance Stabilization Energy (RSE). RSE is defined at the difference in energy between the energy of the hybrid and the estimated energy of the lowest energy resonance contributor. RSE = Ehybrid-Elowest E contributor EX. Which is more stable, methoxide ion or methanoate ion? Page 2 of 3

CHEM 109A Drawing Resonance Structures

O O-

CLAS

The methanoate ion is more stable b/c is has 2 resonance structures (& therefore the hybrid has RSE) whereas methoxide ion has only 1.
O OH OH O

O-

For example 3. Circle the most significant resonance contributor(s) in 1 & 2 above. Some examples of BAD resonance structures & why is each bad X Atoms (nuclei) are not in the same positions not the same connectivity between atoms.

X
The two structures do NOT have the same number of unpaired electrons

( this is an acceptable resonance structure, but it is not common to use these no-bond resonance structures) X These structures can NOT conform to any molecular geometry too much strain
O O-

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