Chem 3053

Organic Chemistry I Klein 1st Ed. Chapter 2 Molecular Representation and Resonance Contributors

R.L. Halterman

This chapter emphasizes the relationship between actual molecules in the flask and how we represent them on paper. We must be able to apply the various rules in order to accurately translate between a three dimensional molecule and a two dimensional drawing. A key aspect is the use of resonance contributors to represent a more conceptual hybrid that is closer to reality, but hard to depict. Important Concepts, Topics and Reactions: Section 2.1Topic Molecular representation starts with molecular formula (no structural detail), condensed structure, partially condensed structure and Lewis structure (with connectivity structural detail). Be able to use all of these. We will later add spatial orientation to the structural drawings. Problems SB2.1, 2.1a-f, 2.2, 2.3 Bond-Line structures are the most common approach to depicting more complicated molecules. Carbon atoms are depicted in zig-zag lines or rings with each end of the line and each vertex representing a carbon. Hydrogen atoms on carbon atoms need not be shown. Enough Hs to fill the octet are implied. Whenever an atomic symbol is used (O, N etc) the Hs on that atom must be shown. Non-bonded lone pairs are implied on those atoms (with any Hs included) to bring up to Lewis octet. It is good form to include Hs on a carbon when you write out the C atomic symbol. Problems: SB2.2, 2.5, 2.6, SB-2.3, 2.8 (as many as needed to be proficient), 2.10 Functional groups are characteristic groups of atoms/bonds that define a set chemical behavior, eg C=C are alkenes, COH are alcohols. Familiarize yourself with the structures and functional group names in Table 2.1. Eventually you will need to know all of these as they are covered. Carbon atoms with formal charges are very important for later reactivity. On any charged species, you should draw in all Hs even in bond-line drawings. This visual cue helps you notice when there are fewer than four bonds to C and thus be able to look for a lone pair (carbanion) or no lone pair (carbocation) Problems. 2.13 Identifying lone pairs is based on producing the correct formal atomic charge given bonding on an atom (with Hs shown). Be able to add lone pairs to bring C, O and N to the given formal charge. Use the rubrics in tables 2.2 and 2.3 to guide you to notice what charge looks correct on O or N given a set number of bonds (eg 2 bonds to O normalneutral, 3 bonds gives cation, one bond gives anion). Problems SB2.4, 2.14, 2.15, SB2.5, 2.16, 2.18, 2.19 Three-dimensional bond-line structures depict the orientation of groups in space. Solid bondlines imply an average position in the plane of the paper, wedged lines imply the attached atom/group is above the plane, dashed lines imply the attached atom/group is below the plane. These depictions are introduced here and will be mastered when we cover stereochemistry in Chpt 5. Recognize Fischer, Haworth and bicyclic depictions. The use of resonance contributors is one of the key concepts in organic chemistry. We have previously depicted an electron pair shared between two atoms in a valence bond model. While this valence bond model is usually sufficient for sigma bonds, we often need a more complete model when dealing with pi-electrons (electrons bonded side-to-side through the p-orbitals). Molecular orbital theory gives an accurate model for delocalization/stabilization of electrons (eg Fig 2.4), but is more difficult to really use at this level. Spreading electrons over more than two atoms can be depicted by drawing two valence bond models (resonance structures) that can be averaged into a resonance hybrid. Although you draw multiple resonance contributors on

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paper, the electrons are not flipping between these formsin the actual molecule, they are spread out. Delocalizing electrons is energetically a good thing, they spend time nearer more nuclei and thus have better Coloumbic attraction. Delocalization of electrons = stabilization. 2.8 Electron movement arrows are used to show the flow of valence electrons (base of arrow = origin of electrons, head of arrow = where they move to). In resonance structures single bonds (electrons in sigma bonds) are not involved. You may move electrons from lone pairs or pibonds onto empty p-orbitals or into pi-bonds (all resonance electrons are in the pi network). Do not exceed Lewis octet by moving electrons toward a filled sp3 atom. It is best to draw out all Hs if you are using a bond-line drawing in order to avoid exceeding octet. Problems: SB2.6 2.21. Formal Charges in resonance structures. Show the proper formal charges in the limiting resonance structures and realize that the real molecule will have charge distribution according the average of these resonance contributors Problems SB2.7, 2.23, 2.24 Pattern / structure recognition. Practice these drawings to get familiar with what the compounds should look like and what sites are resonance active. Allylic carbons are attached to a double bond and electrons on the atom adjacent to a double bond can delocalize through the pi-system. When in doubt on generating resonance structures, separate pi-bond electrons onto one end, or push lone pair toward adjacent double bond, or electrons toward adjacent carbocation. Problems 2.25, 2.26. 2.27, 2.32 Assessing stability/importance of resonance contributors. The hybrid structure most closely resembling the actual electron distribution in a molecule is a weighted average of the contributors. Not all resonance contributors are equally important. The more stable the individual contributor is, the greater its weighting in the hybrid structure. Resonance contributor stability depends on electron stability in those structures: 1) Presence of Lewis octet, 2) minimum charge separation (eg neutral better than zwitterion) and 3) placement of formal charges on most appropriate atoms (eg, negative on more electronegative atoms). Problems SB2.8, 2.33, 2.35 Delocalized pi-electrons vs localized sigma-framework electrons. Resonance delocalization requires the electrons to be in overlapping p-orbitals. Electrons in sp, sp2 or sp3 orbitals or orbital-based bonds do not participate in resonance. Note especially difference in amide Fig 2.6 and pyridine Fig 2.8. Problems SB2.9, 2.36

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Review concepts and terminology p. 87 and SkillBuilder concepts p. 88-89. Assigned Problems for End of Unit Do these problems when you have finished the chapter (or as indicated in lecture). 2.42, 2.43, 2.44, 2.47, 2.49, 2.50, 2.51, 2.55, 2.63, extra challenge 2.65, 2.66, 2.67