Kinetics of Cl(2P) reactions with CF3CHCl2, CF3CHFCl,and CH3CFCl2

The rate coefficients for the removal of Cl atoms by reaction with three HCFCs, CF₃CHCl₂ (HCFC-123), CF₃CHFCl (HCFC-124), and CH₃CFCl₂ (HCFC 141b), were measured as a function of temperature between 276 and 397 K. CH₃CF₂Cl (HCFC-142b) was studied only at 298 K. The Arrhenius expressions obtained are: k₁ = (3.94 ± 0.84)× 10^?12 exp[?(1740 ± 100)/T] cm³ molecule^?1 s^?1 for CF₃CHCl₂ (HCFC 123); k₂ = (1.16 ± 0.41) × 10^?12 exp[?(1800 ± 150)/T] cm³ molecule^?1 s^?1 for CF₃CHFCl (HCFC 124); and k₃ = (1.6 ± 1.1) × 10^?12 exp[?(1800 ± 500)/T] cm³ molecule^?1 s^?1 for CH₃CFCl₂ (HCFC 141b). In case of HCFC 141b, non-Arrhenius behavior was observed at temperatures above ca. 350 K and is attributed to the thermal decomposition of CH₂CFCl₂ product into Cl + CH₂CFCl. In case of HCFC-142b, only an upper limit for the 298 K value of the rate coefficient was obtained. The atmospheric significance of these results are discussed. © 1993 John Wiley & Sons, Inc.     

Unimolecular Rate Constants for the HF and HCl Elimination Reactions from Chemically Activated CF2ClSH

Chemically activated CF₃SH, CFCl₂SH, and CF₂ClSH were formed through combination of SH and CF₃, CFCl₂, and CF₂Cl radicals, respectively. The SH radical was prepared by abstraction of an H‐atom from H₂S by the halocarbon radical produced during photolysis of (CF₃)₂C=O, (CFCl₂)₂C=O, or (CF₂Cl)₂C=O. 1,2‐HX (X = F, Cl) elimination reactions were observed from CF₃SH, CFCl₂SH, and CF₂ClSH with products detected by GC‐MS. The combination reaction of CF₂Cl radicals with SH radicals prepared CF₂ClSH molecules with approximately 318 kJ/mol of internal energy. The experimental rate constants for elimination of HCl and HF from CF₂ClSH were 3 ± 3 × 10¹⁰ and 2 ± 1 × 10⁹ s^?1, respectively. Comparison to Rice–Ramsperger–Kassel–Marcus (RRKM) calculated rate constants assigned the threshold energies as 171 ± 12 and 205 ± 12 kJ/mol for the unimolecular elimination of HCl and HF, respectively. Theoretical calculations using the B3PW91, MP2, and M062X methods with the 6311+G(2d,p) and 6‐31G(d',p') basis sets established that for a specific method the threshold energies differ by only 4 kJ/mol between the two different basis sets. There was wide variation among the three methods, but the M062X approach appeared to give threshold energies closest to the experimental values. Chemically activated CF₃SH and CFCl₂SH were also prepared with about 318 kcal mol^?1 of internal energy, and the HX (X = F, Cl) elimination reactions were observed. Only HCl loss was detected from CFCl₂SH, but the rate was too fast to measure with our kinetic method; however, based on our detection limit the HF elimination channel is at least 50 times slower.     

Isomerisation of CF2ClCH2Cl and CFCl2CH2F by Interchange of Cl and F Atoms with Analysis of the Unimolecular Reactions of Both Molecules

The recombination of CF₂Cl with CH₂Cl and CFCl₂ with CH₂F were employed to generate CF₂ClCH₂Cl* and CFCl₂CH₂F* molecules with 381 and 368 kJ mol^?1, respectively, of vibrational energy in a room‐temperature bath gas. The unimolecular reactions of these molecules, which include HCl elimination, HF elimination, and isomerisation by interchange of chlorine and fluorine atoms, were characterized. The three rate constants for CFCl₂CH₂F were 2.9×10⁷, 0.87×10⁷ and 0.04×10⁷ s^?1 for HCl elimination, isomerisation and HF elimination, respectively. The isomerisation reaction must be included to have a complete characterization of the unimolecular kinetics of CFCl₂CH₂F. The rate constants for HCl elimination and HF elimination from CF₂ClCH₂Cl were 14×10⁷and 0.37×10⁷ s^?1, respectively. Isomerisation that has a rate constant less than 0.08×10⁷ s^?1 is not important. These experimental rate constants were matched to calculated statistical rate constants to assign threshold energies, which are 264, 268, and 297 kJ mol^?1, respectively, for isomerisation, HCl elimination, and HF elimination for CFCl₂CH₂F and 314, 251, and 289 kJ mol^?1 in the same order for CF₂ClCH₂Cl. Density functional theory was used to evaluate the models that were needed for the statistical rate constants; the computational method was B3PW91/6‐31G(d′,p′). Threshold energies for the unimolecular reactions of CF₂ClCH₂Cl and CFCl₂CH₂F are compared to those for CF₂ClCH₃ and CFCl₂CH₃ to illustrate the elevation of threshold energies by F‐ or Cl‐atom substitution at the beta carbon atom (identified by C_H). The DFT calculations systematically underestimate the threshold energy for HCl elimination.     

Substituent effects on the disproportionation-combination rate constant ratios for gas-phase halocarbon radicals. Part III: Reactions of CF3 + CF3CH2 CHCF3 and CF3 CH2CHCF3 + CF3CH2 CHCF3

Disproportionation/combination rate constant ratios, k_d/k_c, for the reactive collision between CF₃CH₂CHX + CF₃ radicals and between CF₃CH₂CHX + CF₃CH₂CHX radicals have been measured for X = CF₃. The k_d/k_c = 0.066 ± 0.013 when H is transferred to the CF₃ radical and 0.125 ± 0.025 for H transfer to the CF₃CH₂CHCF₃ radical. Comparison of these results with previous work shows that X = CF₃ increases the k_c/k_c' s relative to X = Cl or H. The effect of the CF₃ substituent on the disproportionation rate is discussed. © 1996 John Wiley & Sons, Inc.     

Nitroxide chemistry. Part XVII [1]. Reaction of bistrifluoromethyl nitroxide with some halogenoalkanes and related alkenes

The mono (bistrifluoromethylamino-oxy)alkanes (CF₃)₂NOCXYZ (X = Y = F, Z = Cl; X = H, Y = F or Cl, Z = CH₃; X = Y = F, Z = CH₃; X = H, Y = Cl or Br, Z = CF₃; X = Cl, Y = Br, Z = CF₃) have been synthesised by treatment of appropriate halogenoalkanes, CHXYZ, with bistrifluoromethyl nitroxide. The 1,2-bis(bistrifluoromethylamino-oxy)alkanes (CF₃)₂NOCH₂CXYON(CF₃)₂ were obtained as by-products in the reactions involving the ethanes CH₃CHXY (X = H, Y = F or Cl; X = Y = F); these products, like their analogues (CF₃)₂NOCHFCF₂ON(CF₃)₂ and (CF₃)₂NOCH₂CCl₂ON(CF₃)₂, were also prepared $\text{via}$ attack of bistrifluoromethyl nitroxide on the corresponding ethenes.     

Rate constants and Arrhenius parameters for the reactions of Cl atoms with the halogenated ethers: CF3CH2OCHF2, CF3CHClOCHF2, and CF3CH2OCClF2

Rate constants have been determined for the reactions of Cl atoms with the halogenated ethers CF₃CH₂OCHF₂, CF₃CHClOCHF₂, and CF₃CH₂OCClF₂ using a relative‐rate technique. Chlorine atoms were generated by continuous photolysis of Cl₂ in a mixture containing the ether and CD₄. Changes in the concentrations of these two species were measured via changes in their infrared absorption spectra observed with a Fourier transform infrared (FTIR) spectrometer. Relative‐rate constants were converted to absolute values using the previously measured rate constants for the reaction, Cl + CD₄ → DCl + CD₃. Experiments were carried out at 295, 323, and 363 K, yielding the following Arrhenius expressions for the rate constants within this range of temperature:Cl + CF₃CH₂OCHF₂: k = (5.1₅ ± 0.7) × 10⁻¹² exp(−1830 ± 410 K/T) cm³ molecule⁻¹ s⁻¹ Cl + CF₃CHClOCHF₂: k = (1.6 ± 0.2) × 10⁻¹¹ exp(−2450 ± 250 K/T) cm³ molecule⁻¹ s⁻¹ Cl + CF₃CH₂OCClF₂: k = (9.6 ± 0.4) × 10⁻¹² exp(−2390 ± 190 K/T) cm³ molecule⁻¹ s⁻¹ The results are compared with those obtained previously for the reactions of Cl atoms with other halogenated methyl ethyl ethers. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 165–172, 2001     

Kinetic study of gas-phase reactions with CF2Cl2 and CFCl3. Analysis using the transition state theory (TST) of the chlorine atom transfer reactions by CF3 and CH3 radicals from halomethanes

The following gas-phase reactions: were studied by the competitive method with CF₃I as the source of radicals. The kinetic parameters obtained in the temperature range 533–613 K and 503–613 K respectively for chlorine atom transfer reactions are given by: where θ = 2.303 RT (cal mol^?1). The Arrhenius A values were calculated for seven chlorine atom transfer reactions (CF₂Cl₂, CFCl₃, CCl₄ with CF₃ radicals; CF₃Cl, CF₂Cl₂, CFCl₃ and CCl₄ with CH₃ radicals) by using the thermochemical kinetic version of the Transition State Theory (TST).     

Substituent effects on the disproportionation—combination rate constant ratios for gas‐phase halocarbon radicals,Part 5: Reactions of CF3 + CF3CH2CHCH3 and CF3CH2CHCH3 + CF3CH2CHCH3

Rate constant ratios, k_d/k_c for the disproportionation/combination reaction have been measured as 0.07 ± 0.02 when an H is removed from the CH₂ position of the CF₃CH₂CHCH₃ radical and as 0.24 ± 0.03 when the H is removed from the CH₃ position in the reaction with the CF₃ radical. For the self‐reaction between two CF₃CH₂CHCH₃ radicals, k_d/k_c has been measured as 0.27 ± 0.03 when the H is removed from the CH₂ position and as 0.47 ± 0.04 when the H is removed from the CH₃ position. The branching fraction, corrected for the number of hydrogens at each site, is 0.70 favoring the methyl position when the acceptor radical is CF₃ and 0.54 when CF₃CH₂CHCH₃ is the acceptor radical. Branching fraction results show that the CF₃ substituent on the CF₃CH₂CHCH₃ radical hinders disproportionation when CF₃ is the acceptor radical. When the accepting radical is CF₃CH₂CHCH₃ the CF₃ substituent may slightly impede the disproportionation reaction, but the branching ratio is nearly statistical. The effect of substituents on the donor radical, CF₃CH₂CHX, will be discussed for the series X = H, CF₃, Cl, and CH₃ when the acceptor radical is CF₃. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 549–557, 2001     

Darstellung und charakterisierung von (CF3)2PPH2 und (CF3)2AsPH2

(CF₃)₂EPH₂ (E = P,As) may be prepared in high yield by the cleavage of M-P bonds in compounds of the type R₃MPH₂ (M = Si, Ge, Sn) with (CF₃)₂EX (X = Cl, Br, I). The direction of bond fission depends on X and on the reaction temperature. These new compounds may also be obtained, but in lower yield, by the reaction of LiAl(PH₂)₄ with (CF₃)₂EX. Application of the principle of this reaction to other R′₂EX compounds [(CH₃)₂PCl, (CH₃)₂AsI, F₂PX (X = Br, I)] has been investigated. The IR and NMR spectra of the new compounds are reported.     

On the kinetic mechanism of the hydrogen abstraction reactions of the hydroxyl radical with CH3CF2Cl and CH3CFCl2: A dual level direct dynamics study

By means of the dual‐level direct dynamics method, the mechanisms of the reactions, CH₃CF₂Cl + OH → products (R1) and CH₃CFCl₂ + OH → products (R2), are studied over a wide temperature range 200–2000 K. The optimized geometries and frequencies of the stationary points are calculated at the MP2/6‐311G(d,p) level, and then the energy profiles of the reactions are refined with the interpolated single‐point energy method at the G3(MP2) level. The canonical variational transition‐state theory with the small‐curvature tunneling (SCT) correction method is used to calculate the rate constants. For the title reactions, three reaction channels are identified and the H‐abstraction channel is the major pathway. The results indicate that F substitution has a significant (reductive) effect on hydrochlorofluorocarbon reactivity. Also, for all H‐abstraction reaction channels the variational effect is small and the SCT effect is only important in the lower temperature range on the rate constants calculation. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Relative rate constants for reactions of HFC 152a, 143, 143a, 134a,and HCFC 124 with F or Cl atoms and for CF2CH3, CF2HCH2, and CF3CFH radicals with F2, Cl2, and O2

Relative rate experiments using UV photolysis of F₂ or Cl₂ have been used to determine rate constant ratios for several hydrofluorocarbon (HFC) reactions with Cl or F atoms and for HFC alkyl radicals with molecular halogens. For mixtures with F₂ present, dark reactions are, also, observed which are attributed to thermal dissociation of the F₂ to form F atoms. At 296 K, the rate of reaction (1a) [CF₂HCH₃ + F → CF₂CH₃ + HF] relative to (1b) [CF₂HCH₃ + F → CF₂HCH₂ + HF] is k_1a/k_1b = 0.73 (±0.13) and is independent of T (= 262–348 K). At 296 K, the ratio of reaction (2a) [CF₂HCH₂F + F → products] to that of (k_1a + k_1b) is (k_1a + k_1b)/k_2a = 2.7 (±0.4), and for reaction (2b) [CF₃CH₃ + F → products] (k_1a + k_1b)/k_2b = 22 ± 12. The temperature dependence (263–365 K) of the rate constant of reaction (3) [CF₃CFH₂ + Cl → products] relative to reaction (4) [CF₃CFClH + Cl → products] is k₃/k₄(±10%) = 1.55 exp(?300 K/T). For the alkyl radicals formed from HFC 152a (CF₂HCH₂ and CF₂CH₃) and from HFC 134a (CF₃CFH), rate constants for the reactions with F₂ and Cl₂ were measured relative to their reactions with O₂. The rate constant of reaction (5cl) [CF₂CH₃ + Cl₂ → CF₂ClCH₃ + Cl] relative to (5o) [CF₂CH₃ + O₂ → CF₂(O₂)CH₃] is k_5cl/k_5o(±15%) = 0.3 exp(200 K/T). For reaction (5f) [CF₂CH₃ + F₂ → CF₃CH₃ + F], k_5f/k_5o(±35%) = 0.23. The ratio for reaction (6f) [CF₂HCH₂ + F₂ → CF₂HCH₂F + F] relative to (6o) [CF₂HCH₂ + O₂ → CF₂HCH₂O₂] is k_6f/k_6o(±40%) = 1.23 exp(?730 K/T). The rate constant ratio for reaction (8cl) [CF₃CFH + Cl₂ → CF₃CFClH + Cl] relative to reaction (8o) [CF₃CFH + O₂ → CF₃CFHO₂] is k_8cl/k_8o(±18%) = 0.16 exp(?940 K/T). For reaction (8f) [CF₃CFH + F₂ → CF₃CF₂H + F], k_8f/k_8o(±35%) = 0.6 exp(?860 K/T). © 1993 John Wiley & Sons, Inc.     

Substituent effects on the disproportionation-combination rate constant ratios for gas-phase halocarbon radicals. II. Reactions of •CF3 +CF3CH2CH2• and CF3CH2CH2• + CF3CH2CH2•

Disproportionation/combination rate constant ratios, k_d /k_c, have been measured for the collision between CF₃CH₂CH₂ and CF₃ radicals to be 0.022 ± 0.002 and for CF₃CH₂CH₂ and CF₃CH₂CH₂ radicals to be 0.100 ± 0.002. Comparison to previous work from this laboratory for the reaction of CF₃CH₂CHCl with CF₃ radicals shows that substitution of Cl for H increases the k_d /k_c by about 50%; however, for the auto disproportionation-combination of CF₃CH₂CH₂ radicals the chlorine substituent decreases the observed rate constant ratio by a factor of two. The chlorine substituent effect on the observed k_d /k_c ratios is compared to predictions from molecular orbital calculations. © 1996 John Wiley & Sons, Inc.     

Hydrogen abstraction from CF3CF2CFH2 and CF3CFHCF2H by OH radicals and Cl atoms: theoretical enthalpies and rate constants

The hydrogen abstraction reactions of CF₃CF₂CFH₂ and CF₃CFHCF₂H with OH radicals and Cl atoms have been studied theoretically by a dual-level direct dynamics method. Two stable conformers of CF₃CF₂CFH₂ with C _s and C ₁ symmetries and all possible abstraction channels for each reaction are all taken into consideration. Optimized geometries and frequencies of all the stationary points and extra points along minimum-energy path (MEP) have been computed at the BB1K/6-31+G(d, p) level of theory. To refine the energy profile of each reaction channel, single point energy calculations have been performed by the BMC-CCSD method. The rate constants are evaluated by canonical variational transition state theory (CVT) with the small-curvature tunneling correction method (SCT) over a wide temperature range of 200–1,000 K. The detailed branching ratios of four reactions are discussed. The good agreement found between our theoretical rate constants and the available experimental data suggests that the present approach could provide a reliable prediction for the CF₃CFHCF₂H + Cl reaction about which there is little experimental information. The kinetic calculations show that the SCT effect plays an important role in all channels. In addition, in order to further reveal the thermodynamic properties, the enthalpies of formation of the reactants (CF₃CF₂CFH₂ and CF₃CFHCF₂H) and the product radicals (CF₃CF₂CFH, CF₃CFCF₂H, and CF₃CFHCF₂) are evaluated by applying isodesmic reactions at both BMC-CCSD//BB1K/6-31+G(d, p) and MC-QCISD//BB1K/6-31+G(d, p) levels of theory.     

Über Sn[OCH(CF3)2]2 und Sn (OCH2CF3)2 (n = 1, 2)

On S_n[OCH(CF₃)₂]₂ and S_n(OCH₂CF₃)₂ (n = 1, 2) The sulfoxylates S[OCH(R)CF₃]₂, 1 and 2 and the disulfides S₂[OCH(R)CF₃]₂, 5 and 6 (R = CF₃, H) are obtained by reacting SCl₂ or S₂Cl₂, respectively, and the lithium alcoxides LiOCH(R)CF₃. Chlorine and compound 2 give ClS(O)OCH₂F₃ and CF₃CH₂Cl, whereas the sulfur-sulfur bound is cleaved in 5 and 6 furnishing SCI₂, 1 and 2 , respectively. The ¹⁹F n.m.r. spectrum of 5 and the ¹H n.m.r. spectrum of 6 are interpreted in terms of hindered rotation about the sulfur-sulfur axis.     

Kinetic study of the reaction of chlorine atoms with CF3I and the reactions of CF3 radicals with O2, Cl2 and NO at 296 K

The kinetics of the gas-phase reaction of Cl atoms with CF₃I have been studied relative to the reaction of Cl atoms with CH₄ over the temperature range 271–363 K. Using k(Cl + CH₄) = 9.6 × 10^?12 exp(?2680/RT) cm³ molecule^?1 s^?1, we derive k(Cl + CF₃I) = 6.25 × 10^?11 exp(?2970/RT) in which E_a has units of cal mol^?1. CF₃ radicals are produced from the reaction of Cl with CF₃I in a yield which was indistinguishable from 100%. Other relative rate constant ratios measured at 296 K during these experiments were k(Cl + C₂F₅I)/k(Cl + CF₃I) = 11.0 ± 0.6 and k(Cl + C₂F₅I)/k(Cl + C₂H₅Cl) = 0.49 ± 0.02. The reaction of CF₃ radicals with Cl₂ was studied relative to that with O₂ at pressures from 4 to 700 torr of N₂ diluent. By using the published absolute rate constants for k(CF₃ + O₂) at 1–10 torr to calibrate the pressure dependence of these relative rate constants, values of the low- and high-pressure limiting rate constants have been determined at 296 K using a Troe expression: k₀(CF₃ + O₂) = (4.8 ± 1.2) × 10^?29 cm⁶ molecule^?2 s^?1; k_∞(CF₃ + O₂) = (3.95 ± 0.25) × 10^?12 cm³ molecule^?1 s^?1; F_c = 0.46. The value of the rate constant k(CF₃ + Cl₂) was determined to be (3.5 ± 0.4) × 10^?14 cm³ molecule^?1 s^?1 at 296 K. The reaction of Cl atoms with CF₃I is a convenient way to prepare CF₃ radicals for laboratory study. © 1995 John Wiley & Sons, Inc.     

Hydrogen abstraction reactions of OH radicals with CF<Subscript>2</Subscript>ClCClXH (X = F,Cl) and CFCl<Subscript>2</Subscript>CClXH (X = F,Cl): a mechanistic and kinetic study

The reactions of OH (OD) radicals with CF₂ClCClFH (R1), CF₂ClCCl₂H (R2), CFCl₂CClFH (R3), and CFCl₂CCl₂H (R4) have been investigated theoretically by a dual-level direct dynamics method. The optimized geometries and frequencies of the stationary points are calculated at the MPW1K/6-311+G(d,p) level. To improve the reaction enthalpy and potential barrier of each reaction channel, the single-point energy calculation is made by the MC-QCISD method. The enthalpies of formation of the species CF₂ClCClFH, CF₂ClCCl₂H, CFCl₂CClFH, CFCl₂CCl₂H, CF₂ClCClF, CF₂ClCCl₂, CFCl₂CClF, and CFCl₂CCl₂ are evaluated by two sets of isodesmic reactions. Using canonical variational transition state theory (CVT) with the small-curvature tunneling correction (SCT) method, the rate constants of OH and OD radicals with CF₂ClCClXH (X = F, Cl) and CFCl₂CClXH (X = F, Cl) are evaluated over a wide temperature range of 100–2,000 K at the MC-QCISD//MPW1K/6-311+G(d,p) level. The calculated CVT/SCT rate constants are consistent with available experimental data. The results show that the tunneling correction has an important contribution in the calculation of rate constants at lower temperatures. For the above-mentioned four reactions, the kinetic isotope effects are also calculated. Finally, the effect of fluorine or chlorine substitution on reactivity of the C–H bond is discussed.     

Negative ion formation in CF2Cl2, CF3Cl and CFCl3 following low energy (0—10 eV) impact with near monoenergetic electrons

Negative ion formation in CF₂Cl₂, CF₃Cl and CFCl₃ under low-energy electron impact has been investigated using a trochoidal monochromat The ions observed are F^?, Cl^?, FCl^?, Cl₂^?, CFCl₂^? from CF₂Cl₂; F^?, Cl^?, FCl^?, CF₂Cl Quoting available thermochemical data, it can be shown that most of the observed negative ions arise from dissociative attachment processes. Appearance The extremely high yield of Cl^? in CFCl₃, which is observed at ε = 0.0 eV, will be discussed with regard to the lifetime of this molecule i     

Kinetics of the reactions of halogenated methyl radicals (CF3, CF2Cl,CFCl2, and CCl3) with molecular chlorine

The kinetics of four gas-phase reactions involving halogenated methyl radicals (R ? CF₃, CF₂Cl, CFCI₂, and CCI₃) with molecular chlorine have been studied using a tubular reactor coupled to a photoionization mass spectrometer. The radicals were homogeneously generated by the pulsed photolysis of precursor molecules at 193 nm. The subsequent decays of the radical concentration were monitored in real-time experiments as a function of Cl₂ concentration to obtain the rate constants of these R + Cl₂ reactions. Where possible, the rate constants were measured as a function of temperature to determine Arrhenius parameters. Apparent discrepancies between these measured rate constants for CF₃ and CCl₃ with Cl₂ and ones obtained in prior indirect studies are explained. The higher activation energies for these R + Cl₂ reactions compared to that of the CH₃ + Cl₂ reaction are attributed in part to the different polarities of the transition states formed.     

Rate constants for the reactions of OH radicals with CH3OCF2CF3, CH3OCF2CF2CF3, and CH3OCF(CF3)2

The rate constants for the reactions of OH radicals with CH₃OCF₂CF₃, CH₃OCF₂CF₂CF₃, and CH₃OCF(CF₃)₂ have been measured over the temperature range 250–430 K. Kinetic measurements have been carried out using the flash photolysis, laser photolysis, and discharge flow methods combined respectively with the laser induced fluorescence technique. The influence of impurities in the samples was investigated by using gas‐chromatography. The following Arrhenius expressions were determined: k(CH₃OCF₂CF₃) = (1.90) × 10⁻¹² exp[−(1510 ± 120)/T], k(CH₃OCF₂CF₂CF₃) = (2.06) × 10⁻¹² exp[−(1540 ± 80)/T], and k(CH₃OCF(CF₃)₂) = (1.94) × 10⁻¹² exp[−(1450 ± 70)/T] cm³ molecule⁻¹ s⁻¹. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 846–853, 1999     

Reaktion von Chlornitrat mit CF3I: Isolierung von Trifluormethylchloriodnitrat CF3I(Cl)ONO2 und Kristallstruktur von Trifluormethylioddinitrat CF3I(ONO2)2

Reaction of Chlorine Nitrate with CF₃I: Isolation of Trifluormethylchloroiodinenitrate CF₃I(Cl)ONO₂ and the Crystal Structure of Trifluormethyliodinedinitrate CF₃I(ONO₂)₂ CF₃I reacts with ClONO₂ to Iodine(III)-compounds. After an addition CF₃I(Cl)ONO₂ is isolated and characterized by vibrational spectra. With surplus ClONO₂ it is formed CF₃I(ONO₂)₂. CF₃I(ONO₂)₂ crystallizes monoclinic in the space group P2₁/c with the cell parameters a = 1 024.3(6) pm, b = 873.5(6) pm, c = 873.4(6) pm and Z = 4. We measered following bonding distances: I? O: 207.3(3) and 220.8(2) pm, I? C: 221.1(4) pm and N? O: from 119.1(4) to 141.5(3) pm. Through an intermolecular I ··· O-contact the central iodine becomes a distorted plane geometry.