18535-07-4

Upstream product

• 133129-78-9 ONClF⁽¹⁺⁾*AsF₆^(1-) = ONClF(AsF₆) 
• 12005-87-7 N₂F⁽¹⁺⁾*AsF₆^(1-) = (N₂F)AsF₆ 
• 7789-25-5 nitrosyl fluoride 
• 7784-35-2 arsenic(III) fluoride 

Downstream Products

• 7784-36-3 arsenic pentafluoride 

Relevant academic research and scientific papers

The N2F+ cation. An unusual ion containing the shortest presently known nitrogen-fluorine bond

The N2F+AsF6- salt was prepared in high yield from trans-N2F2 by thermal trans-cis isomerization in the presence of AsF5 at 70°C. A displacement reaction between N2F+AsF6- and FNO yields exclusively cis-N2F2. The Lewis acids BF3 and PF5 do not form a stable adduct with cis-N2F2 at temperatures as low as -78°C and do not catalyze the N2F2 trans-cis isomerization. A semiempirical molecular orbital model is used to explain the puzzling differences in the reaction chemistry of cis- and trans-N2F2. The crystal structure of N2F+AsF6- (monoclinic, C2/m, a = 9.184 (5) A?, b = 5.882 (2) A?, c = 5.160 (2) A?, β = 90.47 (4)°, Z = 2) was determined. Alternate space groups (Cm and C2) can be rejected on the basis of the observed vibrational spectra. Since in C2/m the N2F+ cations are disordered, only the sum of the N-F and N-N bond distances could be determined from the X-ray data. Local density functional calculations were carried out for N2F+ and the well-known isoelectronic FCN molecule. The results from these calculations allowed the sum of the N2F+ bond lengths to be partitioned into the individual bond distances. The resulting N-F bond length of 1.217 A? is by far the shortest presently known N-F bond, while the N-N bond length of 1.099 A? is comparable to the shortest presently known N-N bond length of 1.0976 (2) A? in N2. The surprising shortness of both bonds is attributed to the high s-character (sp hybrid) of the σ-bond orbitals on nitrogen and the formal positive charge on the cation. Thus, the shortening of the N-F bond on going from sp3-hybridized NF4+ (1.30 A?) to sp-hybridized N2F+ (1.22 A?) parallels those found for the C-H and C-F bonds in the CH4, CH2=CH2, CH≡CH and CF4, CF2=CF2, FC≡N series, respectively. The oxidative power of N2F+ has also been studied. The N2F+ cation oxidized Xe and ClF to XeF+ and ClF2+, respectively, but did not oxidize ClF5, BrF5, IF5, XeF4, NF3, or O2.

Preparation of the nitryl salts ON(Cl)F+AsF6-, ON(CF3)F+AsF6-, and HON(CH2)CF3+SbF6- and crystal structure of HON(CH2)CF3+AsF6-

The ON(Cl)F+AsF6- and ON(CF3)F+AsF6- salts are prepared by oxidative fluorination of ONCl and ONCF3 with N2F+AsF6-. Methylation of ONCF3 with CH3F and AsF5 gives ON(CH3)CF3+AsF6-, which in the solid state exists as the enol tautomer hydroxylimmonium salt HON(CH2)CF3+AsF6-, triclinic, of space group P1 with a = 5.063 (1) ?, b = 7.757 (3) ?, c = 10.429 (2) ?, α = 86.75 (2)°, β = 89.34 (2)°, and γ = 74.12 (2)°. The framework of the cation is planar, with C-N bond lengths of 147.7 (5) and 127.3 (5) pm and an N-O distance of 137.2(4) pm. The cation and anion have a short H?F contact of 166 (6) pm. An alternative method for the preparation of ONF2+MF6- (M = As, Sb) was found involving the oxidative fluorination of ONF with XeF+MF6-.