Nonclassical carbocation

Schleyer, Olah, and co-workers.55 In this method, the sums of all 13C chemical shifts of carbocations with their respective hydrocarbon precursors are compared. A trivalent carbocation has a sum of chemical shifts of at least 350 ppm higher than the sum for the corresponding neutral hydrocarbon. This difference can be rationalized by partly attributing it to the hybridization change to sp2 and to the deshielding influence of an unit positive charge in the trivalent carbocation. Since higher coordinate carbocations (nonclassical ions) have penta- and hexa-coordinate centers, the sum of their chemical shifts relative to their neutral hydrocarbons is much smaller, often by less than 200 ppm. 

The differentiation of bridged nonclassical from rapidly equilibrating classical carbocations based on NMR spectroscopy was difficult because NMR is a relatively slow physical method. We addressed this question in our work using estimated NMR shifts of the two structurally differing ions in comparison with model systems. Later, this task... 

The discovery of a significant number of hypercoordinate carboca-tions ( nonclassical ions), initially based on solvolytic studies and subsequently as observable, stable ions in superacidic media as well as on theoretical calculations, showed that carbon hypercoordination is a general phenomenon in electron-deficient hydrocarbon systems. Some characteristic nonclassical carbocations are the following. 

It was the study of hypercarbon-containing nonclassical carboca-tions that allowed us to firmly establish carbon s ability in a hydrocarbon system to bind simultneously with five (or six or even seven) atoms or groups. It should be emphasized that carbocations represent... 

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

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

Both acetolyses were considered to proceed by way of a rate-determining formation of a carbocation. The rate of ionization of the ewdo-brosylate was considered normal, because its reactivity was comparable to that of cyclohexyl brosylate. Elaborating on a suggestion made earlier concerning rearrangement of camphene Itydrochloride, Winstein proposed that ionization of the ero-brosylate was assisted by the C(l)—C(6) bonding electrons and led directly to the formation of a nonclassical ion as an intermediate. 

In discussing nonclassical carbocations we must be careful to make the distinction between neighboring-group participation and the existence of nonclassical carbocations. ° If a nonclassical carbocation exists in any reaction, then an ion with electron delocalization, as shown in the above examples, is a discrete reaction intermediate. If a carbon-carbon double or single bond participates in the departure of the leaving group to form a carbocation, it may be that a nonclassical carbocation is involved, but there is no necessary relation. In any particular case, either or both of these possibilities can be taking place. 

The structure of nonclassical carbocations, such as norbomenyl 3, has been the subject of debate since the 1950s when Saul Winstein published his milestone studies on the solvolysis of tosylated norbomenyl compounds. It was proposed that the norbomenyl cation should be represented as the nonclassical structure 4+, with a 3-center, 2-electron cyclic system (3c-2e), rather than as the classical equilibrium... 

For historical overviews on the 2-norbornyl cation, the bicyclobutonium ion and related hypercoordinated carbocations see (a) Nonclassical Ions, Reprints and Commentary, P. D. Bartlett, W.A. Benjamin, Inc, New York and Amsterdam 1965 (b) The Nonclassical Ion Problem, Brown, H.C. with comments by Schleyer, P.v.R. Plenum Press, New York, 1977... 

The l3C NMR spectrum of the C4H7+ cation in superacid solution shows a single peak for the three methylene carbon atoms (72) This equivalence can be explained by a nonclassical single symmetric (three-fold) structure. However, studies on the solvolysis of labeled cyclopropylcarbinyl derivatives suggest a degenerate equilibrium among carbocations with lower symmetry, instead of the three-fold symmetrical species (13). A small temperature dependence of the l3C chemical shifts indicated the presence of two carbocations, one of them in small amounts but still in equilibrium with the major species (13). This conclusion was supported by isotope perturbation experiments performed by Saunders and Siehl (14). The classical cyclopropylcarbinyl cation and the nonclassical bicyclobutonium cation were considered as the most likely species participating in this equilibrium. 

The prototypical pentacoordinated carbocation, the parent nonclassical carbocation, CH, 1, has been extensively studied in the gas phase as well as by theoretical calculations.Among the higher coordinate carbocations, the hexacoordinated methylium dication, 2, and heptacoordinated trication, 3, were also shown to be energy minima by ab initio calculations. High-level ab initio calculations show that they have C2V and Csv structures, respectively.Their isoelectronic boron analogs were also studied. 

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