The Nuclear Warfare Chain Letter II - ACS Publications - American

difference provides an excellent case history for the psy- chology of scientists. The 2-norbornyl cation was originally presented to me as the least a...
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CORRESPONDENCE The 2-Norbornyl Cation Revisited I read the two letters by Dewar and by Olah in the recent issue with considerable interest and amusement.lY2 While I agree with almost all of Dewar’s comments, it is fascinating to compare the positions taken by these authors with the original position for the 2-norbornyl cation. The difference provides an excellent case history for the psychology of scientists. The 2-norbornyl cation was originally presented to me as the least ambiguously known case for a nonclassical It was then the position that a-bridging between C-2 (the cationic center) and C-6 (the transannular carbon) was very powerful, so powerful as to distort the structure from the unsymmetrical one of the classical form to a new symmetrical one, designated the nonclassical structure. The large stabilization postulated to be provided by a-bridging in the transition state for solvolysis of the exo isomer and its absence in the endo isomer provided the generally accepted explanation for the high exo/endo rate ratio. The symmetrical structure for the intermediate provided the explanation for the racemization accompanying the solvolysis of optically active 2-norbornyl derivatives. The magnitude of this stabilization was considered to be huge. Calculated values for nonclassical stabilization of 50 kcal/mo14 and 39 kcal/mo15 were accepted without question.6 Goering demonstrated that there must be a difference in the energies of the exo and endo transition states of 6.0 kcal/mol to account for the high exo/endo rate ratios observed in ~olvolysis.~ This provides a firm experimental basis for the magnitude of the proposed nonclassical stabilization-6.0 kcal/mol in the solvolytic transition state for the exo and -8 kcal/mol for the fully developed cation. Comparisons of the heats of ionization of tertiary benzylic chlorides vs. the corresponding secondary in three representative systems (Cp = cyclopentyl and Nb = norbornyl), PhMe2CC1/2-PrC1, 1-PhCpCl/CpCl, 2-Ph-emNbCllexo-NbC1, fail to show any significant difference between the three system^.^ There is no evidence for a stabilization of 8.0 kcal/mol in secondary 2-norbornyl, not present in the highly stabilized classical62-phenyl-2-norbornyl cation. Small stabilizations of 1-2 kcal/mol cannot be ruled out. They are within the uncertainties of the data. But, to retain perspective, such stabilizations are comparable to weak van der Waals interactions. The data clearly establish the absence of 6 kcal/mol of stabilization in the transition state and 8 kcal/mol in the fully developed cation. Therefore, the stabilization originally postulated to account for the high exozendo rate ratio cannot be confirmed experimentally. As pointed out by Dewar’ and Kramer,8 Olah’s own ESCA spectrag support a nonsymmetrical structure for the 2-norbornyl cation. Both Dewar’ and Olah2 now conclude that the 2-norbornyl cation is not symmetrical. But they argue that because the cation is “delocalized”it should be considered nonclassical. But all carbonium ions are delocalized. The high stability of the tert-butyl cation was attributed to delocalization (hyperconjugation) as long ago as 1943.1° Such “delocalization” has never been considered to be a synonym for “nonclassical”. The fact is that the large stabilization required by the 0001-4842/86/0119-0034$01.50/0

original explanation is not found e~perimentally.~ The symmetry required by the nonclassical structure is ruled out by the ESCA result^.^ If authors wish to continue using the term for a species which has neither the large stabilization nor the symmetry of the original proposed structure, we cannot stop them. However, we can enjoy the spectacle. Herbert C. Brown Purdue University (1) Dewar, M. J. S. Acc. Chem. Res. 1985,18, 292. (2) Olah, G. A.; Prakash, G. K. S. Acc. Chem. Res. 1985, 18, 292. (3) Brown, H. C. Acc. Chem. Res. 1983, 16, 432. (4) Trahanovsky, W. S. J. Org. Chem. 1965,30, 1666. (5) Klopman, G. J. Am. Chem. SOC.1969, 91, 89.

(6)Olah, G. A.; White, A. M.; De Member, J. R.; Commeryras, A,; Liu, C. Y. J. Am. Chem. SOC.1970,92,4627. (7) Goering, H.L.;Schewene, C. B. J. Am. Chem. SOC.1965,87, 3516. (8) Kramer. G. Adu. Phvs. Ow. Chem. 1975. 11. 177. (9) Olah, GI A.; Mateesiu, G. D.; Riemenschneider, J. J . Am. Chem. SOC.1972,94, 2529. (10) Remick, A. E. ‘Electronic Interpretation of Organic Chemistry”; Wiley: New York, 1943.

Happiness Is a Legitimate Research Project Contrary to popular belief the quest for legitimacy, so important in the humanities and the social and political sciences, does not stop at the door of the chemistry lab. In fact, a cursory check of the opening sentences of chemical research papers reveals two schools of thought, the we-are-doing-something-nobody-else-doeslegitimation &e., “Virtually nothing is known about X; thus we decided to investigate X...”) and the we-are-doing-the-samething-as-everybody-else legitimation (i.e., “The current increased interest in Y prompts us to report...”). It is intriguing to speculate whether these extremes touch, i.e., if just about any research project could be accommodated within these two categories, or whether there is a third category. Probably a chemist who wrote an opening sentence going like ”In our desire to add to the meager, but steady trickle of papers concerning 2 we wish to report ...” would be made to wash his mouth with soap by irate taxpayers and/or referees. Alexander Senning Aarhus University Denmark

The Nuclear Warfare Chain Letter I1 While catching up on back issues of Accounts recently, I came across Dr. Bunnett’s editorial on the nuclear warfare chain letter.’ It brought to mind a somewhat analogous effort 37 years ago that is still relevant to the times. Albert Einstein and a number of other prominent Americans published a letter2 warning about a notorious mideast terrorist, also described as a fascist and a racist, who had formed a political party and was seeking American support. Within a few decades, the constituency of this terrorist, which was explicitly compared by Einstein

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et al. to the followers of Hitler and Mussolini, had elected him to national leadership, and his country was receiving unprecedented levels of American political and financial backing. If, on one hand, Einstein and coauthors were completely wrong about the terrorist, who came to be treated with the same regard as other world leaders, then it follows that scientists are not necessarily credible predictors of what constitutes a social danger. On the other hand, if the individuals who signed the letter were right, the outcome shows that public warnings even by the most eminent scientific authorities may go completely unheeded. Should scientists, now in greater numbers than back then, revive this unfinished business that was Einstein’s concern? Rather than amplifying mass anxieties, isn’t a more important contribution of scientists the dispassionate insights that run counter to them, with academic tenure a provision for affording some measure of immunity from the often hostile consequences of expressing those insights? Although I never received an antinuclear letter (circulated among productive, leading figures, it was saidperhaps the chain length, even with branching, was short?), I wonder how much substance they really contained. Were any of the chain-propagatingunits acquainted with the late

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English mathematician Lewis Fry Richardson’s work on the relationship of arms expenditures to war? I wonder if his work is not cited by antinuclear activists because it does not support what seems to be a central thesis: that the nuclear arsenals of the superpowers, because of their enormous size, constitute the greatest danger. To which authority do we appeal? I do have some concern about nuclear war because I see plausible mechanisms for it to happen. For instance, a western power overcommitted to a low-grade democracy in a dispute with an older form of government, the latter willing to risk bringing the world down rather than endure further losses to elected neonazis. This mechanism is independent of a fractional reduction in the arms level of the superpowers. In the event of the latter I will be uncomfortable if scientists or the public become complacant and decide that these mechanisms are not worthy of attention. G . David Mendenhall

Michigan Technological University (1) Bunnett, J. F. Acc. Chem. Res. 1985, 18, 159. (2) Einstein, A. et al. The New York Times, Dec. 4, 1948.

0 1986 American Chemical Society