Schleyer, Paul von Rague (Author)
Mainz, Vera V. (Author)
Strom, E. Thomas (Author)
American Chemical Society
Volume: 1209
Pages: 139-168
The proposal by Winstein and Trifan that the 2-exo-norbornyl cation has a bridged, non-classical structure initiated a number of investigations into this system. In 1962, H. C. Brown entered into the fray by proposing a pair of rapidly-equilibrating cations and steric effects as alternative explanations. The 2-norbonyl cation was investigated via rate studies, nmr experiments, theoretical calculations, and other methods over a number of years by a number of workers. While the X-ray determination of the 2-exo-norbornyl structure by Scholz et al. (Science, 2013, 341, 62) brought long overdue closure to the vituperative structure controversy, this chapter summarizes other remarkable issues currently engaging research groups worldwide. Unexpectedly, Duncan et al.’s gas phase protonation of norbornene gives the 1,3-dimethylcyclopentyl cation, the C7H11+ global minimum. Merino et al.’s molecular dynamics simulations reveal many acyclic as well as monocyclic intermediates along the reaction pathway. Finally, the 2-endo-norbornyl cation also has a bridged minimum, but “leakage” to the 2-exo cation has a very low barrier. This bridging of the 2-endo cation explains products found from the reaction of α-pinene with acetic acid. Thus, even at this late date, norbornyl cation isomers still fascinate.
...MoreBook E. Thomas Strom; Vera V. Mainz (2016) The Foundations of Physical Organic Chemistry: Fifty Years of the James Flack Norris Award.
Similar Citations
Chapter
Kenneth B. Wiberg;
(2015)
My Study of Optical Activity - From the Distant Past to the Present with Stops in-Between
Chapter
Ronald Breslow;
(2015)
A Life in Physical Organic Chemistry
Book
E. Thomas Strom;
Vera V. Mainz;
(2016)
The Foundations of Physical Organic Chemistry: Fifty Years of the James Flack Norris Award
Article
Barry W. Ninham;
(2017)
The Biological/Physical Sciences Divide, and the Age of Unreason
Article
Weininger, Stephen J.;
(2000)
“What's in a Name?” From Designation To Denunciation: The Nonclassical Cation Controversy
Chapter
Edward M. Arnett;
(2015)
Some Thermochemical Studies of Solvation from the 1960s and 1970s
Article
Rowlinson, J. S.;
(2010)
James Joule, William Thomson and the Concept of a Perfect Gas
Thesis
James, Jeremiah Lewis;
(2008)
Naturalizing the Chemical Bond: Discipline and Creativity in the PaulingProgram, 1927--1942
Article
Gal, Joseph;
(2011)
Louis Pasteur, Language, and Molecular Chirality: Background and Dissymmetry
Article
Eberhart, Mark;
Travis, Jones;
(2013)
The Two Faces of Chemistry: Can They Be Reconciled?
Article
Causá, Mauro;
Savin, Andreas;
Silvi, Bernard;
(2014)
Atoms and Bonds in Molecules and Chemical Explanations
Chapter
Arthur Greenberg;
(2015)
James Flack Norris: His Early Contributions to Physical Organic Chemistry
Book
Manuel DeLanda;
(2015)
Philosophical Chemistry: Genealogy of a Scientific Field
Article
Martin Saltzman;
(2015)
A Pioneering Course in Physical Organic Chemistry: J. W. Baker's 1942 Third-Year Lectures to Undergraduates
Chapter
Kathleen M. Trahanovsky;
E. Thomas Strom;
(2015)
Exploring Free Radicals: The Life and Chemistry of Glen A. Russell
Article
Gortler, Leon B.;
Saltzman, Martin D.;
(1998)
Paul D. Bartlett's Chem 17a: A pioneer course in physical organic chemistry
Chapter
Andrew Streitwieser;
(2015)
Hydrogen Isotopes in Physical Organic Chemistry
Book
Anders Lennartson;
(2021)
Carl Wilhelm Scheele and Torbern Bergman: The Science, Lives and Friendship of Two Pioneers in Chemistry
Article
Fisher, Grant;
(2006)
The Autonomy of Models and Explanation: Anomalous Molecular Rearrangements in Early Twentieth-Century Physical Organic Chemistry
Article
Wisniak, Jaime;
(2002)
Fritz Haber---A Conflicting Chemist
Foundations of Chemistry
Chirality: The Pharmacological, Biological, and Chemical Consequences of Molecular Asymmetry
Indian Journal of History of Science
Notes and Records: The Royal Society Journal of the History of Science
Studies in History and Philosophy of Science
Be the first to comment!