New Dioxygenyl Compounds

Abstract

Notes 457 which is close to the value reported in the gas phase,6 2.010. The measured N14 and F19 couplings are 16 and 56 gauss, respectively. ExperimentalThe sieves used in these experiments were Linde6 Molecular Sieves in powdered form. They were heated to 300°and then evacuated at 10~6 atm. prior to the introduction of N2F4 vá 2NF2.The e.p.r. spectra reported herein were obtained with a Varían V-4502 e.p.r. spectrometer system employing 100-kc./sec. modulation and detection. The n.m.r. spectra reported were obtained with a Varían Associates V4300 40-Mc./sec. spectrometer. The sample cells were 5-mm. o.d. and 7 in. long capped by side arms and a Fischer-Porter7 pressure valve for loading the cells with gas.Caution.-N2F4 reacts with Linde Molecular Sieve 10X at room temperature and pressures greater than 0.5 atm. Occasionally we have had samples explode with both 10X and 13X sieves. It is our belief, however, that by vigorous outgassing at 300°and by vigorous exclusion of air these systems may be handled safely.Acknowledgments.-This work was carried out under Contract No. DA-01-021 ORD-11878 (Z) Mod. No. 7. (5) L.

Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry

“…The latter method is elegant, as the cation is synthesized in the same reaction step as the WCA. For example, the compounds O 2 [BF 4 ] and O 2 [PF 6 ] can be prepared by fluoride transfer from O 2 F 2 to BF 3 or PF 5 accompanied by the release of 0.5 equiv of elemental fluorine [5] . The complexes [M(CO) 6 ] 2+ 2 [BF 4 ] − (M=Fe, Ru, Os) are accessible through oxidation of [M 3 (CO) 12 ] with F 2 in anhydrous HF (aHF) and subsequent reaction with CO and HF/BF 3 [6] .…”

“…For example, the compounds O 2 [BF 4 ]a nd O 2 [PF 6 ]c an be preparedb yf luoride transfer from O 2 F 2 to BF 3 or PF 5 accompanied by the release of 0.5 equiv of elemental fluorine. [5] The complexes [M(CO) 6 ] 2 + 2[BF 4 ] À (M = Fe, Ru, Os) are accessible through oxidation of [M 3 (CO) 12 ]w ith F 2 in anhydrous HF (aHF) and subsequentr eaction with CO and HF/BF 3 . [6] However,B F 3 and PF 5 are gases with low boiling points anda re extremelys ensitive towards moisture, which makes handling of these substancesi nt he laboratory difficult.…”

Paradoxes and paradigms: on ambisaline ions of oxygen, fluorine, and related oxyfluorides

“…There are numerous dioxygenyl salts, most generally containing univalent anions with fluorine, an exquisitely highly electronegative and most reactive element among all elements, and central atom(s) most typically in their highest oxidation state consistent with being an anion. These anions include [BF 4 ] − [5,6] and [Sb 2 F 11 ] − [7,8] and as found in the first example of these dioxygenyl species, [PtF 6 ] − [9,10]. Dioxygenyl salts with oxygen-containing counterions are notably absent.…”

“…The assertion that [O 2 ] 2+ is unstable by bond cleavage is true but not particularly surprising nor relevant. Most doubly charged polyatomic cations are intrinsically unstable [16] except as found in the condensed phase [17] [5,6]. The [O 2 F] + remains within the purview of the mass spectroscopist [18,19], and the theorist and wishful synthetic chemist [20,21].…”

Modern Views on the Nature of Inorganic Peroxy-compounds

“…The formation of the O2 ion is accompanied by the evolution of 286 kcal mole" 1 and the energy of dissociation into O + + Ο is 153.48 ± 0.05 kcal mole" 1 . 92 The interatomic distance in the OJ molecular ion, which is formed on removal of one electron from the VTI* level, is reduced to 1.1227 A compared with 1.2074 A in the oxygen molecule, while, as stated above, on formation of peroxide anions the above distance increases owing to the introduction of additional electrons in the same level 93 .…”