Norbornyl

One of the major contemporary chemical controversies in which I was inadvertently involved developed in the 1950s, surprisingly over the structnre of a deceptively simple seven carbon-containing bicyclic carbocation, the 2-norbornyl (bicyclo[2.2.1]heptyl) cation. The in-... 

Winstein, one of the most brilliant chemists of his time, concluded that it is attractive to account for these results by way of the bridged (non-classical) formulation for the norbornyl cation involving accelerated rate of formation from the exo precursor [by anchimeric assistance His formulation of the norbornyl cation as a cr-bridged species stimulated other workers in the solvolysis field to interpret results in a variety of systems in similar terms of rr-delocalized, bridged carbonium... 

In 1965 he stated, On the other hand, the norbornyl cation does not possess sufficient electrons to provide a pair for all of the bonds required by the proposed bridged structures. One must propose a new bonding concept, not yet established in carbon structures (emphasis added). 

The Brown-Winstein nonclassical ion controversy can be summed up as differing explanations of the same experimental facts (which were obtained repeatedly and have not been questioned) of the observed significantly higher rate of the hydrolysis of the 1-exo over the 2-endo-norbornyl esters. As suggested by Winstein, the reason for this is participation of the Ci-Q single bond leading to delocalization in the bridged nonclassical ion. In contrast. Brown maintained that the... 

Nonclassical ions, a term first used by John Roberts (an outstanding Caltech chemist and pioneer in the field), were defined by Paul Bartlett of Harvard as containing too few electrons to allow a pair for each bond i.e., they must contain delocalized (T-electrons. This is where the question stood in the early 1960s. The structure of the intermediate 2-norbornyl ion could only be suggested indirectly from rate (kinetic) data and observation of stereochemistry no direct observation or structural study was possible at the time. 

I still did not have suitable low-temperature instrumentation of my own to carry out the low-temperature NMR studies, but Martin Saunders at Yale did. Thus our samples now traveled the Massachusetts Turnpike from Boston to New Haven, where with Marty we were able to study solutions of the norbornyl cation at increasingly lower temperatures using his home-built variable-temperature NMR instrumentation housed in the basement of the old Yale chemistry building. We... 

Figure 9.1. 395 MHz M NMR spectra of 2-iiorbornyl 50 MHz proton decoupled C NMR spectra cation in SbF5/S02CIF/S02F2 solution of 2-norbornyl cation ( C enriched) in SbF5/S02ClF/S02F2 solution.

As mentioned, we also carried out IR studies (a fast vibrational spectroscopy) early in our work on carbocations. In our studies of the norbornyl cation we obtained Raman spectra as well, although at the time it was not possible to theoretically calculate the spectra. Comparison with model compounds (the 2-norbornyl system and nortri-cyclane, respectively) indicated the symmetrical, bridged nature of the ion. In recent years, Sunko and Schleyer were able, using the since-developed Fourier transform-infrared (FT-IR) method, to obtain the spectrum of the norbornyl cation and to compare it with the theoretically calculated one. Again, it was rewarding that their data were in excellent accord with our earlier work. 

Figure 9.2. Carbon Is photoelectron spectrum Is core-hole-state spectra for the 2-norbornyl cation of tert-butyl cation and Clark s simulated spectra for the classical and nonclassical ions.

As the norbornyl ion controversy evolved, it became a highly public and frequently very personal and bitter pnblic debate. Saul Winstein suddenly died in the fall of 1969, shortly after the Salt Lake City sym-posinm. To my regret, I seemed to have inherited his role in repre-... 

Clearly there was no lack of devoted adversaries (perhaps a more proper term than enemies) on both sides of the norbornyl ion controversy. It is to their credit that we today probably know more about the structure of carbocations, such as the norbornyl cation, than about most other chemical species. Their efforts also resulted not only in rigorous studies but also in the development or improvement of many techniques. Although many believe that too much effort was expended... 

During my studies 1 realized that the formation of the cr-delocalized 2-norbornyl cation from 2-norbornyl precursors represented the equiv-... 

Niels Bohr was frequently quoted to have said, you must be prepared for a surprise, but at the same time you must also understand what your findings mean and what they can be used for. To me, this is the lesson of the norbornyl ion controversy. I strongly believe it was not a waste of effort to pursue it, and eventually it greatly helped to advance chemistry to new areas of significance that are still emerging. 

The most studied hypercoordinate carbocation is the 2-norbornyl cation, around which the nonclassical ion controversy centered (Chapter 9). 

The formation of the (X-delocalized norbornyl cation via ionization of 2-norbornyl precusors in low-nucleophilicity, superacidic media, as mentioned, can be considered an analog of an intramolecnlar Friedel-Crafts alkylation in a saturated system. Indeed, deprotonation gives nortricyclane,... 

SECTION 5.12. THE NORBORNYL CATION AND OTHER NONCLASSICAL CARBOCATIONS... 

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