Paradoxes and paradigms: on ambisaline ions of oxygen, fluorine, and related oxyfluorides
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ORIGINAL RESEARCH
Paradoxes and paradigms: on ambisaline ions of oxygen, fluorine, and related oxyfluorides Maja Ponikvar-Svet 1 & Kathleen F. Edwards 2 & Joel F. Liebman 3 Received: 15 October 2020 / Accepted: 28 October 2020 # Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract In this review, we discuss different ions of oxygen and fluorine and related oxyfluorides and isoelectronic species from the viewpoint of their potential ambisaline character, defined as a property of species X so that both X+ and X− may both be found in isolable salts. The term is applied to the ions as well as to the neutral precursor. Reactivity versus stability, reported and plausible synthetic approaches of well-established and probable species are discussed from the perspective of thermochemistry. Keywords Ambisaline . Oxygen . Fluorine . Halogens . Thermochemistry
Introduction The prefix “ambi” generally means “two,” “both,” and “on both sides” as found in the words ambidextrous, ambiguous, and ambivalent. The prefix “amphi” has a meaning related to ambi, e.g., amphiprotic compounds can both donate and accept a proton, amphihydric refers to some compound RH that can transfer a hydride ion, hydrogen atom, or proton to result in a reactive species stable enough to be generated in solution and amphiphilic compounds which possess both hydrophilic and lipophilic properties. The word “amphiphilic” can be also used for a species that has both nucleophilic and electrophilic behavior. The term “ambisaline” is used to describe a species X so that X+ and X− may both be found in isolable salts, albeit very often not with commonplace counterions [1, 2]. Thus, both cation and anion salts are known. The term ambisaline * Joel F. Liebman [email protected] Maja Ponikvar-Svet [email protected] Kathleen F. Edwards [email protected] 1
Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia
2
Doctor of Business Administration Program, The Graduate School, University of Maryland Global Campus, Largo, MD 20774, USA
3
Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD 21250, USA
can as such also be considered as a manifestation of the trichotomy of convenience, anthropocentrism, and folksonomy [1, 3, 4]. In the present review, we will focus on ambisaline ions of oxygen. Our discussion will be extended also to fluorine, related oxyfluorides, and some isoelectronic species.
2-Oxygen species (species with two oxygens) A particularly rich, yet simple, example of ambisaline ions and derived salts is that derived from O 2 . The wellestablished ions are the singly positively charged ion, [O2]+, known as the dioxygenyl cation, and the singly and doubly charged anions, [O2]− and [O2]2−, known as superoxide and peroxide, respectively. There are numerous dioxygenyl salts, most generally containing univalent anions with fluorine, an exquisitely highly electronegative and most reactive element among all elements,
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