A Half‐Century Odyssey in the Realm of Reactive Intermediates

Abstract

Through a retrospective examination of the author’s half‐century immersion in physical organic chemistry, an attempt is made to identify some broader currents in the field. Among these are the cyclical nature of physical organic chemistry, the persistence of research themes, the driving force of new instrumentation, paradigm shifts in theory, greater computational power, enhanced time resolution of experiments, and the export of mechanism‐based analysis to other foci of contemporary science.

Criegee Intermediates Beyond Ozonolysis: Synthetic and Mechanistic Insights

“…With the advancement of sophisticated experimental methods for generation, and characterization techniques,m ost fleeting intermediates can be illuminated for timescales of 10 3 ms, ms, ns,p s, and fs, timescales that were only postulated in the early days of physical organic chemistry. [126] In the last few years,intensive efforts have been dedicated to innovative synthetic methods for CI generation, characterization, and investigations on their reactivity.N ew experimental techniques have been developed for the generation of CIs and for examining their chemical structures as well as properties.The direct detection of CIs in the gas phase and their precise spectroscopic characterization have provided in-depth details on their nature,lifetime,reactivity,and electronic structure,and have shown that they have as ubstantial zwitterionic rather than abiradical character.…”

Adventures in Reactive Intermediate Chemistry: A Perspective and Retrospective

“…I now conclude with several personal impressions and observations. A related discussion recently appeared in the Israel Journal of Chemistry …”

“…As I noted elsewhere, our research “is not like a railway journey, wherein the destination is known once you purchase your ticket and board the train. Our science is more like those voyages of exploration made by our ancestors to the fringes of the world, where unknown islands and new species were to be found beyond the breadth of the chart.”…”

“…In the interest of concision, I omit discussions of our extensive research on micelles, liposomes, and phosphate ester cleavage, offering only several references as examples. Also, there is necessarily some overlap with a “scientific autobiography” published in early 2016 …”

Criegee‐Intermediate über die Ozonolyse hinaus: Ein Einblick in Synthesen und Mechanismen

“…www.angewandte.de gung und Charakterisierung konnten die flüchtigsten Zwischenprodukte in Zeiteinheiten von 10 3 ms, ms, ns,p su nd fs nachgewiesen werden, die in den frühen Tagen der physikalischen organischen Chemie nur postuliert wurden. [126] In den letzten Jahren wurde intensiv an innovativen Synthesemethoden zur Erzeugung von CIs,deren Charakterisierung und Untersuchungen zu ihrer Reaktivitätg earbeitet. Es wurden neue experimentelle Techniken zur Erzeugung von CIs und zur Untersuchung ihrer chemischen Strukturen sowie ihrer Eigenschaften entwickelt.…”