Cations KrF+, XeOF3 +, XeF3 +, and XeOF5 + and oxidizing properties of KrF+

McKee, D. E.; Adams, Christopher J.; Zalkin, A.; Bartlett, Neil

doi:10.1039/c39730000026

Cited by 38 publications

(24 citation statements)

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“…The molecular cations in these compounds include the dihalogen I 2 + , 67 the fluorocations TeF 3 + , 68 IF 4 + , 69 BrF 4 + , 70 XeF + , 71 and XeF 3 + , 72 70 where D 4h symmetry seems to be retained; however, the structure determination is of low accuracy (R ) 0.14). In addition, the SbF 4 planes are distorted and F t SbF b angles are usually ∼85°, with displacement toward the bridging fluorine.…”

Section: ) Was Added Inmentioning

confidence: 98%

Syntheses and Vibrational and¹³C MAS-NMR Spectra of Bis(carbonyl)mercury(II) Undecafluorodiantimonate(V) ([Hg(CO)₂][Sb₂F₁₁]₂) and of Bis(carbonyl)dimercury(I) Undecafluorodiantimonate ([Hg₂(CO)₂][Sb₂F₁₁]₂) and the Molecular Structure of [Hg(CO)₂][Sb₂F₁₁]₂

et al. 1996

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The synthesis of bis(carbonyl)mercury(II) undecafluorodiantimonate(V), [Hg(CO)(2)][Sb(2)F(11)](2), and that of the corresponding mercury(I) salt [Hg(2)(CO)(2)][Sb(2)F(11)](2) are accomplished by the solvolyses of Hg(SO(3)F)(2) or of Hg(2)F(2), treated with fluorosulfuric acid, HSO(3)F, in liquid antimony(V) fluoride at 80 or 60 degrees C, respectively, in an atmosphere of CO (500-800 mbar). The resulting white solids are the first examples of metal carbonyl derivatives formed by a post-transition element. Both salts are characterized by FT-IR, FT-Raman, and (13)C-MAS-NMR spectroscopy. For [Hg(CO)(2)][Sb(2)F(11)], unprecedentedly high CO stretching frequencies (nu(av) = 2279.5 cm(-)(1)) and stretching force constant (f(r) = 21.0 +/- 0.1) x 10(2) Nm(-)(1)) are obtained. Equally unprecedented is the (1)J((13)C-(199)Hg) value of 5219 +/- 5 Hz observed in the (13)C MAS-NMR spectrum of the (13)C labeled isotopomers at delta = 168.8 +/- 0.1 ppm. The corresponding values (nu(av) = 2247 cm(-)(1), f(r) = (20.4 +/- 0.1) x 10(2) Nm(-)(1), (1)J((13)C-(199)Hg) = 3350 +/- 50 Hz and (2)J((13)C-(199)Hg) 850 +/- 50 Hz) are found for [Hg(2)(CO)(2)][Sb(2)F(11)](2), which has lower thermal stability (decomposition point in a sealed tube is 140 degrees C vs 160 degrees C for the Hg(II) compound) and a decomposition pressure of 8 Torr at 20 degrees C. The mercury(I) salt is sensitive toward oxidation to [Hg(CO)(2)][Sb(2)F(11)](2) during synthesis. Both linear cations (point group D(infinity)(h)()) are excellent examples of nonclassical (sigma-only) metal-CO bonding. Crystal data for [Hg(CO)(2)][Sb(2)F(11)](2): monoclinic, space group P2(1)/n; Z = 2; a = 7.607(2) Å; b = 14.001(3) Å; c = 9.730(2) Å; beta = 111.05(2) degrees; V = 967.1 Å(3); T = 195 K; R(F) = 0.035 for 1983 data (I(o) >/= 2.5sigma(I(o))) and 143 variables. The Hg atom lies on a crystallographic inversion center. The Hg-C-O angle is 177.7(7) degrees. The length of the mercury-carbon bond is 2.083(10) Å and of the C-O bond 1.104(12) Å respectively. The structure is stabilized in the solid state by a number of significant secondary interionic Hg- - -F and C- - -F contacts.

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Section: ) Was Added Inmentioning

confidence: 98%

Syntheses and Vibrational and¹³C MAS-NMR Spectra of Bis(carbonyl)mercury(II) Undecafluorodiantimonate(V) ([Hg(CO)₂][Sb₂F₁₁]₂) and of Bis(carbonyl)dimercury(I) Undecafluorodiantimonate ([Hg₂(CO)₂][Sb₂F₁₁]₂) and the Molecular Structure of [Hg(CO)₂][Sb₂F₁₁]₂

et al. 1996

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“…(2)] by using Fourier transform ion cyclotron resonance (FT-ICR) spectrometry. [14] The NF 2 ions were prepared in the external source of the instrument by electron impact ionization of NF 3 , [15] transferred into the resonance cell, isolated, thermalized by unreactive collisions with pulsed-in argon, and allowed to react with CO. The only ionic product observed was FCO , which was unambiguously identified by exact mass measurements, and the efficiency of the reaction was 0.02 from the ratio of the experimental rate constant and the collision rate constant, estimated as 7.67 Â 10 À10 cm 3 molecule À1 s À1 from average dipole orientation theo-ry.…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Aspects of F+ Transfer Reactions: A Model Study in the Gas Phase

1998

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CO) intermediates involved in this process, which were observed by chemical ionization experiments, were structurally characterized by collisionally activated dissociation spectrometry, and their unimolecular decomposition processes were probed by mass-analyzed ion kinetic energy spectrometry. The results of these experiments are discussed in terms of the potential energy profile obtained by investigating the potential energy surfaces of singlet and triplet (NF 2 CO), as well as the hyperline corresponding to their intersection. Our findings provide probably the first detailed description of the mechanism of a formally simple F transfer reaction. They also have mechanistic implications for related oxidative fluorination reactions in solution, which have been extensively investigated in the last thirty years.

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“…Unlike their xenon analogues, the majority of these salts decompose below room temperature; however, several, including KrF þ AsF À 6 , KrF þ SbF À 6 ; KrF þ Sb 2 F À 11 , KrF þ PtF À 6 , and KrF þ AuF À 6 , are stable at room temperature for appreciable amounts of time. The KrF þ cation is among the most powerful chemical oxidants known (191) and is capable of oxidizing gaseous xenon to XeF þ 5 ; gaseous oxygen to O þ 2 ; NF 3 to NF þ 4 (189); and chlorine, bromine, and iodine pentafluorides to the ClF þ 6 , BrF þ 6 , and lF þ 6 cations, respectively (189,190,(192)(193)(194). (105,195).…”

Section: Krypton Compoundsmentioning

confidence: 99%

Noble‐Gas Compounds

Schrobilgen

Brock

Mercier

2012

Kirk-Othmer Encyclopedia of Chemical Technology

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Noble‐gas reactivity was discovered on March 23, 1962 when Neil Bartlett (1932–2008) showed that xenon gas was oxidized by PtF 6 . The product obtained by Bartlett was initially formulated as XePtF 6 . Pursuant to his discovery, numerous xenon and krypton compounds were synthesized in macroscopic quantities. Among the noble‐gas elements, xenon has the most extensive chemistry, and it can possess formal oxidation states of 0, +2, +4, +6, and +8 in its compounds by forming fluorides, oxides, and oxide fluorides, as well as derivatives in which xenon is bonded to polyatomic groups through oxygen, nitrogen, and carbon. In addition, compounds containing Xe–Au, Xe–Xe, Xe–Cl, and Hg–Xe bonds are known. Other xenon‐element bonds are known in the gas phase or in low‐temperature matrices, which are exemplified by Xe–H, Xe–Si, Xe–S, Xe–X (X=Cl, Br, I), and Xe–U bonds. Krypton chemistry is more limited. Only compounds with krypton in the +2 oxidation state are known, namely, KrF 2 , salts of the KrF + and Kr 2 F 3 + cations, by analogy with xenon, the Kr–O bonded compound, Kr(OTeF 5 ) 2 , and several species containing Kr–N bonds. Several gas‐phase and matrix‐isolated species in which krypton is bonded to carbon, hydrogen, and halides other than fluorine are also known. Radon is believed to form RnF 2 and RnF + by analogy with krypton and xenon. The only argon species that are known are the ArF + cation, which has been observed in the gas phase, and HArF, which has been stabilized in a low‐temperature argon matrix. To date, no argon, neon, or helium compounds have been isolated in macroscopic amounts. Noble‐gas compounds have been used as oxidizers and as oxidative fluorinating agents in chemical syntheses.

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Cations KrF+, XeOF3 +, XeF3 +, and XeOF5 + and oxidizing properties of KrF+

Abstract: The XeOF5+ ion (prepared with KrF+ as oxidizer) is related to XeOF,+; the latter is in turn related to XeF,+, the geometry of which has been established by X-ray crystallography.

Cited by 38 publications

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Syntheses and Vibrational and¹³C MAS-NMR Spectra of Bis(carbonyl)mercury(II) Undecafluorodiantimonate(V) ([Hg(CO)₂][Sb₂F₁₁]₂) and of Bis(carbonyl)dimercury(I) Undecafluorodiantimonate ([Hg₂(CO)₂][Sb₂F₁₁]₂) and the Molecular Structure of [Hg(CO)₂][Sb₂F₁₁]₂

Syntheses and Vibrational and¹³C MAS-NMR Spectra of Bis(carbonyl)mercury(II) Undecafluorodiantimonate(V) ([Hg(CO)₂][Sb₂F₁₁]₂) and of Bis(carbonyl)dimercury(I) Undecafluorodiantimonate ([Hg₂(CO)₂][Sb₂F₁₁]₂) and the Molecular Structure of [Hg(CO)₂][Sb₂F₁₁]₂

Mechanistic Aspects of F+ Transfer Reactions: A Model Study in the Gas Phase

Noble‐Gas Compounds

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Cations KrF+, XeOF3 +, XeF3 +, and XeOF5 + and oxidizing properties of KrF+

Abstract: The XeOF5+ ion (prepared with KrF+ as oxidizer) is related to XeOF,+; the latter is in turn related to XeF,+, the geometry of which has been established by X-ray crystallography.

Cited by 38 publications

References 0 publications

Syntheses and Vibrational and13C MAS-NMR Spectra of Bis(carbonyl)mercury(II) Undecafluorodiantimonate(V) ([Hg(CO)2][Sb2F11]2) and of Bis(carbonyl)dimercury(I) Undecafluorodiantimonate ([Hg2(CO)2][Sb2F11]2) and the Molecular Structure of [Hg(CO)2][Sb2F11]2

Syntheses and Vibrational and13C MAS-NMR Spectra of Bis(carbonyl)mercury(II) Undecafluorodiantimonate(V) ([Hg(CO)2][Sb2F11]2) and of Bis(carbonyl)dimercury(I) Undecafluorodiantimonate ([Hg2(CO)2][Sb2F11]2) and the Molecular Structure of [Hg(CO)2][Sb2F11]2

Mechanistic Aspects of F+ Transfer Reactions: A Model Study in the Gas Phase

Noble‐Gas Compounds

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Syntheses and Vibrational and¹³C MAS-NMR Spectra of Bis(carbonyl)mercury(II) Undecafluorodiantimonate(V) ([Hg(CO)₂][Sb₂F₁₁]₂) and of Bis(carbonyl)dimercury(I) Undecafluorodiantimonate ([Hg₂(CO)₂][Sb₂F₁₁]₂) and the Molecular Structure of [Hg(CO)₂][Sb₂F₁₁]₂

Syntheses and Vibrational and¹³C MAS-NMR Spectra of Bis(carbonyl)mercury(II) Undecafluorodiantimonate(V) ([Hg(CO)₂][Sb₂F₁₁]₂) and of Bis(carbonyl)dimercury(I) Undecafluorodiantimonate ([Hg₂(CO)₂][Sb₂F₁₁]₂) and the Molecular Structure of [Hg(CO)₂][Sb₂F₁₁]₂