Search for the ionic cope rearrangement

Wigfield, Donald C.; Feiner, Steve; Taymaz, Kevser

doi:10.1016/s0040-4039(01)84466-x

Cited by 9 publications

(1 citation statement)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Such a mechanism has been proposed for the Cope rearrangement of 4 (Scheme 3). 6 Another example is the ionic 1,5-shift in 5, 7 where an alkyl cation migrates on to a cyclopentadienyl ring. In these examples, charges in the proposed ionic intermediates are efficiently spread over suitably located heteroatom substituents.…”

Section: Historical Contextmentioning

confidence: 99%

Structural dependence of heterolytic bond dissociation energy of carbon–carbon σ bonds in hydrocarbons

Kitagawa

Takeuchi

1998

J. Phys. Org. Chem.

View full text Add to dashboard Cite

The coordination of a resonance-stabilized hydrocarbon cation and anion yielded a series of unprecedented hydrocarbons, which are susceptible to thermal heterolytic cleavage of carbon-carbon s bonds in polar media, generating the original ions under reversible conditions. When the component ions were sufficiently stabilized, some ion pairs were even isolated as solids, thus providing the first examples of hydrocarbon salts. The direct observation of the heterolysis by means of spectroscopy permitted reliable thermodynamic treatments of the observed degree of ionic dissociation. Correlation of the free energy of heterolysis with solvent dielectric constants and parameters of ion stabilities such as pK HA , pK R and redox potentials revealed the importance of the thermodynamic stabilities of ions, the degree of solvation and steric congestion in the starting molecule as major controlling factors in the heterolysis.

show abstract

Section: Historical Contextmentioning

confidence: 99%