Superelectrophiles and Their Chemistry contains, for the first-time, a discussion of the basics of this emerging field of organic chemistry, alongside tools to help the reader apply the chemistry. Specific tools include an evaluation of the ways to increase the strength of electrophiles, the classification of superelectrophiles, the solvation issues, a review of methods for studying superelectrophilicity, with details of the superelectrophiles that have been identified and studied. Additional information includes substituent effects in activation of superelectrophiles, and solvation in chemical reactions, as well as an insightful look into future applications.

This thesis details the research conducted on the synthesis and reactivity of superelectrophilic di- and polycation salts based on 2-DMAP I. The reaction of 2-DMAP I and 1,3-diiodopropane II proceeded unexpectedly to give products III-V, thought to occur via a dicationic intermediate. Investigation of the reaction conditions allowed for the successful synthesis of 2-DMAP disalt VII from 2- DMAP I and ditriflate VI. This represents the first time such a dication species has been synthesised and isolated. Based on the 2-DMAP unit, a variety of superelectrophile disalts have been synthesised (VIII-X) and characterised. 2-DMAP disalt VII showed enhanced reactivity over its monocationic counterparts XI and XII in the methylation of triphenylphosphine. In the 1:1 competition reaction with dimethyl sulfate in the methylation of triethylamine, 2-DMAP disalt VII and 2- dimethylaminopyrimidine disalt VIII showed greater reactivity than dimethyl sulfate, with disalt VIII being over 2.5 times more reactive. The reactivity of 2-DMAP disalt VII towards hydrogenation was also examined. It was found that in the presence of palladium on activated carbon (1 mol%), disalt VII underwent regiospecific hydrogenation (or deuteration) in the 2-position to give pyridinium disalt XIII (or XIV in the case of deuteration). In this case, 2-DMAP disalt VII showed similar reactivity to the substrate CH≡H4MPT+ in the [Fe]-hydrogenase enzyme. This significantly enhanced reactivity over monocationic salts provides support for the proposal that superelectrophilic activation of CH≡H4MPT+ in the enzyme active-site may contribute to the observed reaction of CH≡H4MPT+ with hydrogen gas. Superelectrophile trisalt XV was also synthesised. This trisalt showed slightly decreased reactivity compared to dimethyl sulfate in the methylation of triethylamine. The high reactivity of the tricationic species was tempered by the dimethylamino group in the 4-position, which served to decrease the reactivity by delocalising the positive charge on the pyridinium ring nitrogen. Amidine disalts XVI and XVII based on amides have also been synthesised. Isolation of these superelectrophiles provides some evidence that such species may exist as intermediates in a variety of synthetic reactions cited in this work. Disalt XVI was shown to be an effective reagent for the formylation of anisole under mild conditions. The synthesis and isolation of these superelectrophile disalts based on the 2-DMAP unit shows that highly reactive superelectrophiles can be obtained using standard laboratory conditions, which considerably widens the scope for synthesis and investigation of such species.

The autobiography of a Nobel Prize winner, this book tells us about George Olah's fascinating research into extremely strong superacids and how it yielded the common term "magic acids." Olah guides us through his long and remarkable journey, from Budapest to Cleveland to Los Angeles, with a stopover in Stockholm. This updated autobiography of a Nobel Prize winner George A. Olah: Chronicles the distinguished career of a chemist whose work in a broad range of chemistry areas, and most notably that in methane chemistry, led to technologies that impact the processing and utility of alternative fuels Is based on Olah's work on extremely strong superacids and how they yielded the common term, "magic acids" Details events since the publication of the first edition in 2000 Inspires readers with details on Dr. Olah's successful recent research on methanol, intended to help provide a solution to "the oil problem"

The chemistry of superacids has developed in the last two decades into a field of growing interest and importance. Now available in a new expanded second edition, this definitive work on superacids offers a comprehensive review of superacids and discusses the development of new superacid systems and applications of superacids in the promotion of unusual reactions. Covering Bronsted and Leurs superacids, solid superacids, carbocations, heterocations, and catalyzed reactions, this timely volume is invaluable to professionals, faculty, and graduate students in organic, inorganic, and physical chemistry.

Organized to enable students and synthetic chemists to understand and expand on aromatic reactions covered in foundation courses, the book offers a thorough and accessible mechanistic explanation of aromatic reactions involving arene compounds. • Surveys methods used for preparing arene compounds and their transformations • Connects reactivity and methodology with mechanism • Helps readers apply aromatic reactions in a practical context by designing syntheses • Provides essential information about techniques used to determine reaction mechanisms