424 Chapter 15 Solutions to Problems 1. 2 a, In the case of 9 pairs of m electrons, there are 18 electrons. Therefore, 4n+2 = 18andn = 4. b. Because it has an odd number of pairs of 7 electrons, it will be aromatic if it is cyclic, planar, and if every atom in the ring has a p orbital b, © @, and g are aromatic b is aromatic, because itis cyclic, planar, every atom in the ring has a p orbital, and it has seven pairs of m electrons. cis aromatic, because it is cyclic, planar, every atom in the ring has a p orbital, and it has three pairs of m electrons. eis aromatic, because it is cyclic, planar, every atom in the ring has a p orbital, and it has nine pairs of m electrons. gis aromatic, because it is cyclic, planar, every atom in the ring has a p orbital, and it has five pairs of 7 electrons. a is not aromatic, because it has (wo pairs of 7 electrons. 4 is not aromatic, because it has two pairs of m electrons and every atom in the ring does not have ap orbital not aromatic, because it has two pairs of 7 electrons and every atom in the ring does not have ap orbital his not aromatic, because it is not cyclic. a. Solved in the text. b, There are five monobromophenanthrenes Br RH OR). Br’Chapter 15 425 4. To be aromatic, a compound must be cyclic and planar, every atom in the ring must havea p orbital, and the 7 cloud must contain an odd number of pairs of electrons. {10]-Annulene is cyclic, every atom in the ring has a p orbital, and it has the correct number of 7 electrons to be aromatic (ive pairs). Knowing it is not aromatic, we can conclude that it is not planar. [12]-Annulene has an even number of pairs of 7 electrons (six pairs) in its m cloud, so it cannot be aromatic. 7 IN NH np ts 3 AO G ye 6. a, The nitrogen atom (the atom at the bottom of the epm) in pyrrole has a partial positive charge because it donates electrons by resonance into the ring. b. The nitrogen atom (the atom at the bottom of the epm) in pyridine has is the most electronegative atom in the molecule. . The relatively electronegative nitrogen atom in pyridine withdraws electrons from the ring. 7. Cyclopentadiene has a lower pX'y. When cyclopentadiene loses a proton, a relatively stable aromatic compound is formed. When cycloheptatriene loses a proton, an unstable antiaromatic ‘compound is formed (Section 15.5). It is, therefore, easier to lose a proton from cyclopentadiene. O — 78 HH —> + HH HW” antiaromatic426 Chapter 15 8. a. 1. Notice that each resonance contributor has a charge of -1. b. 1, five ring atoms 2, four ring atoms 9. a, The three resonance contributors marked with an X are the least stable because in these contributors the two negative charges are on adjacent carbons. 1b. Because these contributors are the least stable, they make the smallest contribution to the hybrid. CFD O- @ —CY—