In organic chemistry, the term norbornyl cation (equivalent with bicyclo-[2.2.1]heptyl cation) describes any of three carbocations formed from norbornane derivatives. Though 1-norbornyl and 7-norbornyl cations have been studied, the most extensive studies and vigorous debates have been centered around the exact structure of the 2-norbornyl cation.
The 2-norbornyl cation has been formed from a variety of norbornane derivatives and reagents. First reports of its formation and reactivity published by Saul Winstein sparked controversy over the nature of its bonding, as he invoked a three-center two-electron bond to explain the stereoselectivity of the resulting product. Herbert C. Brown challenged this assertion on the grounds that classical resonance structures could explain the stereospecificity without needing to adapt a new perspective of bonding.
Evidence of the non-classical nature of the 2-norbornyl cation grew over the course of several decades, mainly through spectroscopic data gathered using methods such as Nuclear magnetic resonance (NMR). Crystallographic confirmation of its non-classical nature did not come until quite recently.
The nature of bonding in the 2-norbornyl cation incorporated many new ideas into the field’s understanding of chemical bonds. Similarities can be seen between this cation and others, such as boranes.
- 1 Theory
- 2 History
- 3 X-ray crystallography
- 4 Experiments
- 5 See also
- 6 References
- 7 External links
The nature of bonding in the 2-norbornyl cation was the center of a vigorous, well-known debate in the chemistry community through the middle of the twentieth century. While the majority of chemists believed that a three-centered two-electron bond best depicted its ground state electronic structure, others argued that all data concerning the 2-norbornyl cation could be explained by depicting it as a rapidly equilibrating pair of cations.
At the height of the debate, all chemists agreed that the delocalized picture of electron bonding could be applied to the 2-norbornyl cation. But this did not answer the fundamental question on which the debate hinged. Researchers continued to search for novel ways to determine whether the three-centered delocalized picture described a low-energy transition state (saddle point on the multidimensional potential energy surface) or a potential energy minimum in its own right. Proponents of the “classical” picture believed that the system was best described by a double-well potential with a very low barrier, while those in the “non-classical” camp envisioned the delocalized electronic state to describe a single potential energy well.
Hypovalency: The Non-Classical Picture
Advocates of the non-classical nature of the stable 2-norbornyl cation typically depict the species using either resonance structures or a single structure with partial bonds (see Figure 2). This hypovalent interaction can be imagined as the net effect of i) a partial sigma bond between carbons 1 and 6, ii) a partial sigma bond between carbons 2 and 6, and iii) a partial pi bond between carbons 1 and 2. Each partial bond is represented as a full bond in one of the three resonance structures or as a dashed partial bond if the cation is depicted through a single structure.
There has been some debate over how much the pi-bonded resonance structure actually contributes to the delocalized electronic structure. Through 1H and 13C NMR spectroscopy, it has been confirmed that little positive charge lies on methylene carbon 6. This is unsurprising as primary carbocations are much less stable than secondary carbocations. However, the 2-norbornyl cation can be formed from derivatives of β-(Δ3-cyclopentenyl)-ethane, indicating that the pi-bonded resonance structure is significant.
The 2-norbornyl cation was one of the first examples of a non-classical ion. Non-classical ions can be defined as organic cations in which electron density of a filled bonding orbital is shared over three or more centers and contains some sigma-bond character.  The 2-norbornyl cation is seen as the prototype for non-classical ions. Other simple cations such as protonated acetylene (ethynium, C
3), protonated ethylene (ethenium, C
5), and protonated ethane (ethanium, C
7) have been shown to be best described as non-classical through infrared spectroscopy. 
The most frequently proposed molecular orbital depiction of the 2-norbornyl cation is shown in Figure 3. Two p-type orbitals, one on each of carbons 1 and 2, interact with a sp3-hybridized orbital on carbon 6 to form the hypovalent bond. Extended Hückel Theory calculations for the 2-norbornyl cation suggest that the orbital on carbon 6 could instead be sp2-hybridized, though this only affects the geometry of the geminal hydrogens.
Rapid Equilibrium: The Classical Picture
According to proponents of a classical double-well potential, the 2-norbornyl cation exists in dynamic equilibrium between two enantiomeric asymmetric structures. The delocalized species central to the non-classical picture is merely a transition state between the two structures. Wagner-Meerwein rearrangements are invoked as the mechanism that converts between the two enantiomers (see Figure 4).
Efforts to isolate the asymmetric species spectroscopically are typically unsuccessful. The major reason for this failure is reported to be extremely rapid forward and reverse reaction rates, which indicate a very low potential barrier for interconversion between the two enantiomers. 
Nortricyclonium: Another Non-classical Structure
Some chemists have also considered the 2-norbornyl cation to be best represented by the nortricylconium ion, a C3-symmetric protonated nortricyclene. This depiction was first invoked to partially explain results of an 14C isotope scrambling experiment. The molecular orbital representation of this structure involves an in-phase interaction between sp2-hybridized orbitals from carbons 1, 2 and 6 and the 1s atomic orbital on a shared hydrogen atom (see Figure 5).
"'Non-classical ions'" differ from traditional cations in their electronic structure: though chemical bonds are typically depicted as the sharing of electrons between two atoms, stable non-classical ions can contain three or more atoms that share a single pair of electrons. In 1939, Thomas Nevell and others attempted to elucidate the mechanism for transforming camphene hydrochloride into isobornyl chloride. In one of the proposed reaction mechanisms depicted in the paper, the positive charge of an intermediate cation was not assigned to a single atom but rather to the structure as a whole. This was later cited by opponents of the non-classical description as the first time that a non-classical ion was invoked. However, the term “non-classical ion” did not explicitly appear in the chemistry literature until over a decade later, when it was used to label delocalized bonding in a pyramidal, butyl cation.
The term synartetic ion was also invoked to describe delocalized bonding in stable carbocations before the term non-classical ion was in widespread use. The first users of this term commented on the striking similarity between bonding in these types of cations and bonding in borohydrides.
First Non-classical Proposals
In 1949, Saul Winstein observed that 2-exo-norbornyl brosylate (p-bromobenzenesulfonate) and 2-endo-norbornyl tosylate (p-toluenesulfonate) gave a racemic mixture of the same product, 2-exo-norbornyl acetate, upon acetolysis. Since tosylates and brosylates work equally well as leaving groups, he concluded that both the 2-endo- and 2-exo- substituted norbornane must be going through a common cationic intermediate with a dominant exo- reactivity. He reported that this intermediate was most likely a symmetric, delocalized 2-norbornyl cation.  It was later shown via vapor phase chromotography that the amount of the endo- epimer of product produced was less than .02%, proving the high stereoselectivity of the reaction.
When a single enantiomer of 2-exo-norbornyl brosylate undergoes acetolysis, no optical activity is seen in the resulting 2-exo-norbornyl acetate (see Figure 7).  Under the non-classical description of the 2-norbornyl cation, the plane of symmetry present (running through carbons 4, 5, and 6) allow equal access to both enantiomers of the product, resulting in the observed racemic mixture.
It was also observed that the 2-exo- substituted norbornanes reacted 350 times faster than the corresponding endo- isomers. Anchimeric assistance of the sigma bond between carbons 1 and 6 was rationalized as the explanation for this kinetic effect. Importantly, the invoked anchimeric assistance led many chemists to postulate that the energetic stability of the 2-norbornyl cation was directly due to the symmetric, bridged structure invoked in the non-classical explanation. However, some other authors offered alternative explanations for the high stability without invoking a non-classical structure.
In 1951, it was first suggested that the 2-norbornyl cation could actually be better described when viewed as a nortricyclonium ion. It has been shown that the major product formed from an elimination reaction of the 2-norbornyl cation is nortricyclene (not norbornene), but this has been claimed to support both non-classical ion postulates.
Herbert C. Brown: A Dissenting View
Herbert C. Brown did not believe that it was necessary to invoke a new type of bonding in stable intermediates to explain the interesting reactivity of the 2-norbornyl cation. Criticizing many chemists for disregarding past explanations of reactivity, Brown argued that all of the aforementioned information about the 2-norbornyl cation could be explained using simple steric effects present in the norbornyl system.  Given that an alternative explanation using a rapidly equilibrating pair of ions was valid for describing the 2-norbornyl cation was valid, he saw no need to invoke a stable, non-classical depiction of bonding. Invoking stable non-classical ions was becoming commonplace; Brown felt that this was not only unwarranted but also counterproductive for the field of chemistry as a whole. Indeed, many papers reporting stable non-classical ions were later retracted for being unrealistic or incorrect. After publishing this controversial view in 1962, Brown began a quest to find experimental evidence incompatible with the delocalized picture of bonding in the 2-norbornyl cation.
Brown also worked to prove the instability of a delocalized electronic structure for the 2-norbornyl cation. If the non-classical ion could be proven to be higher in energy than the corresponding classical ion pair, the non-classical ion would only be seen as a transition state between the two asymmetric cations.  Though he did not rule out the possibility of a delocalized transition state Brown continued to reject the proposed reflectional symmetry of the 2-norbornyl cation, even late in his career.
The introduction of the three-centered two-electron delocalized bond invoked in the non-classical picture of the 2-norbornyl cation allowed chemists to explore a whole new realm of chemical bonds. Chemists were eager to apply the characteristics of hypovalent electronic states to new and old systems alike (though several got too carried away). One of the most fundamentally important concepts that emerged from the intense research focused around non-classical ions was the idea that electrons already involved in sigma bonds could be involved with reactivity. Though filled pi orbitals were known to be electron donors, chemists had doubted that sigma orbitals could function in the same capacity. The non-classical description of the 2-norbornyl cation can be seen as the donation of an electron pair from a carbon-carbon sigma bond into an empty p-orbital of carbon 2. Thus this carbocation showed that sigma-bond electron donation is as plausible as pi-bond electron donation.
The intense debate that followed Brown’s challenge to non-classical ion proponents also had a large impact on the field of chemistry. In order to prove or disprove the non-classical nature of the 2-norbornyl cation, chemists on both sides of the debate zealously sought out new techniques for chemical characterization and more innovative interpretations of existing data. One spectroscopic technique that was further developed to investigate the 2-norbornyl cation was Nuclear Magnetic Resonance (NMR) spectroscopy of compounds in highly acidic media. Comparisons of the 2-norbornyl cation to unstable transition states with delocalized electronic states were often made when trying to elucidate whether the norbornyl system was stable or not. These efforts motivated closer investigations of transition states and vastly increased the scientific community’s understanding of their electronic structure. In short, vigorous competition between scientific groups led to a extensive research and a better understanding of the underlying chemical concepts.
Though characterization of 2-norbornyl cation crystals may have significantly precluded further debates about its electronic structure, it does not crystallize under any standard conditions. Recently, the crystal structure has been obtained and reported through a creative means: addition of aluminum tribromide to 2-norbornyl bromide in dibromomethane at low temperatures afforded crystals of [C
2. By examining the resulting crystal structure, researchers were able to confirm that the crystalline geometry best supports the case for delocalized bonding in the stable 2-norbornyl cation. Bond lengths between the "bridging" carbon 6 and each of carbons 1 and 2 were found to be slightly longer than typical alkane bonds. According to the non-classical picture, one would expect a bond order between 0 and 1 for these bonds, signifying that this explains the crystal structure well. The bond length between carbons 1 and 2 was reported as being between typical single and double carbon-carbon bond lengths, which agrees with non-classical predictions of a bond order slightly above 1. According to the non-classical picture, one would expect a bond order between zero and one for the first two bonds. Investigators who crystallized the 2-norbornyl cation commented that the cation proved impossible to crystallize unless provided a chemical environment that locked it into one definite orientation.
Further evidence for the non-classical model was obtained by tracer studies in which two carbon atoms in the norbornyl skeleton were replaced by the radioactive carbon 14 isotopes (Scheme 4). The primary solvolyis reaction product was derivatized by reduction with lithium aluminium hydride and oxidation with sodium permanganate to the dicarboxylic acid followed by a Curtius rearrangement expelling carbon dioxide. When the acetyl anion is indeed able to attack both C1 and C2 positions of the symmetrical norbornyl cation 2 then 50% of the generated CO2 will contain 14C. The experimental value in this experiment was 40% and in order to account for the presence of 14C in other positions (a scrambling process) the nortricyclonium cation was postulated which is basically a face-capped norbornyl cation allowing hydride shifts.
In 1964 George A Olah began to produce direct evidence for the norbornyl cation when he subjected the norbornyl antimony chloropentafluoride salt obtained by reaction of exo-2-chloro-norbornane with antimony pentafluoride to NMR analysis. The room temperature NMR spectrum was a single broad peak due to the presence of hydride shifts but these could be partially frozen when cooled to −60 °C in liquid sulfur dioxide. It was also found that the norbornyl cation could also be generated from norbornanes with chlorine substituent at the bridging position or bridgehead positions and from reaction of norbornene with HSbF6 thereby confirming the presence of the rearrangements taking place in the 14C scrambling process.
Solid-state NMR analysis was possible at temperatures as low as 5 kelvin at which temperature all positions are assumed to be frozen. One of the two signals visible in the spectrum corresponded to the identical C1 and C2 carbon atoms.
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