The Nonclassical Ion Problem [Paperback]

1. That Fascinating Nonclassical Ion Problem.- 1.1. Introduction.- 1.2. Origins.- 1.3. The Nonclassical Ion Era.- 1.4. Steric Assistance.- 1.5. An Alternative Interpretation.- 1.6. The Rococo Period of Carbonium Ion Structures.- 1.7. Difficulties in Challenging an Accepted Theory.- 1.8. Further DifficultiesA Soft Theory.- 1.9. Still Further DifficultiesSelective Reviews.- 1.10. Conclusion.- Comments.- 2. Steric Assistance in Solvolytic Processes.- 2.1. Introduction.- 2.2. Steric Assistance in the Solvolysis of Highly Branched Alkyl Derivatives.- 2.3. Steric Assistance in the Relative Effects of Methyl and tert-Butyl Groups.- 2.4. Steric Effects in Norbornyl Derivatives.- 2.5. Steric Effects in Ring Systems.- 2.6. Conclusion.- Comments.- 3. ?ParticipationA Factor in Fast Rates?.- 3.1. Introduction.- 3.2. n-, ?- and ?-Participation.- 3.3. ?-Participation and Fast Rates.- 3.4. ?-Participation vs. Steric Assistance.- 3.5. Steric AssistanceNot ?-Participation.- 3.6. The Fast Rates of Exo-Norbornyl and Cyclopropylcarbinyl.- Comments.- 4. Carbon-Bridged Cations.- 4.1. Introduction.- 4.2. What Is a Nonclassical Ion?.- 4.3. ?-Bridging vs. Hyperconjugation.- 4.4. Static Classical, Equilibrating Classical, or ?-Bridged Cations.- 4.5. Stereochemistry and ?-Bridged Cations.- 4.6. ?-and Aryl-Bridged Cations.- 4.7. Conclusion.- Comments.- 5. The Cyclopropylcarbinyl Cation.- 5.1. Introduction.- 5.2. Exceptionally Fast Rates of Solvolysis.- 5.3. Rearrangements in the Solvolysis of Cyclopropylcarbinyl Derivatives.- 5.4. ?-Bridged Structures for the Cation.- 5.5. Stereochemical Characteristics.- 5.5. Conclusion.- Comments.- 6.The 2-Norbornyl Cation.- 6.1. Introduction.- 6.2. Nonclassical Structures for the 2-Norbornyl Cation.- 6.3. Basic Facts.- 6.4. Transition State or Intermediate.- 6.5. Equilibrating Cations.- 6.6. Are Exo Rates Unusually Fast?.- 6.7. Do the High Exo:Endo Rate Ratios Require ?-Bridged Cations?.- 6.8. Do the High Exo:Endo Product Ratios Require ?-Bridged Cal#-