Reactive intermediates solid state studies

A bridged carbocation with a two-electron, three-centre bond was proposed as early as 1939 (Nevell et al., 1939) for the 2-norbornyl cation [lO ] as a reactive intermediate in the solvolysis of 2-norbornyl system (see also Winstein and Trifan, 1949). It has now been isolated as the SbFe salt and the bridged structure is accounted for using solid-state nmr studies... 

Effective charge and transition-state structure in solution, 27, 1 Effective molarities of intramolecular reactions, 17,183 Electrical conduction in organic solids, 16,159 Electrochemical methods, study of reactive intermediates by, 19, 131 Electrochemical recognition of charged and neutral guest species by redox-active receptor molecules, 31, 1... 

The generation of carbocations in strongly acidic media, and the characterization of their structure by NMR in the 1950s was a breathtaking accomplishment that led to the award of the Nobel Prize in Chemistry to George Olah. Over the past 50 years NMR spectroscopy has evolved as the most important experimental method for the direct study of structure and dynamics of carbocations in solution and in the solid state. Hans-Ullrich Siehl provides an excellent review of computational studies to model experimental NMR spectra for carbocations. This chapter provides an example of how the fruitful interplay between theory and experiment has led to a better understanding of an important class of reactive intermediates. 

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