The matrix-isolated molecular complexes CO/XF (X=Cl,Br,I) and the molecular structure of FC(O)Br

García, Pablo Andrés; Willner, Helge; Oberhammer, Heinz; Francisco, Joseph S.

doi:10.1063/1.1814634

Cited by 7 publications

(3 citation statements)

References 19 publications

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“…FC(O)Br and FC(O)Cl have been photolysed in low-temperature matrices. 271 The products are CO and XF (X = Cl or Br) which recombine to form XFÁ Á ÁCO complexes. From FC(O)Cl only one isomer-OCÁ Á ÁClF-is seen but from FC(O)Br three isomers-OCÁ Á ÁBrF, OCÁ Á ÁFBr and COÁ Á ÁBrF-are all seen.…”

Section: Groups 15-17mentioning

confidence: 99%

Chemistry in low-temperature matrices

Almond

Goldberg

2007

Annu. Rep. Prog. Chem., Sect. C: Phys. Chem.

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the Progress of Chemistry, Section C. The report is divided into sections: weak adducts and conformational isomers; reactions of atoms; high-temperature molecules; photochemistry; biological molecules; astrochemistry. The last two sections reflect the fact that matrix isolation now extends into areas outside the traditional mainstream disciplines of chemistry. There are a number of areas where substantial progress has been made during the period of this report. First, the routine use of laser-ablation to generate atoms and to initiate atomic reactions in matrices has increased the scope of matrix isolation to synthesise many new molecular species in inorganic chemistry. Laser-ablation allows ground state atoms to be more easily studied than is the case when atoms are produced by thermal methods. Moreover, this procedure allows atoms to be generated from materials where thermal production is difficult. Secondly, the manufacture of more efficient closed-cycle helium refrigerators allows hydrogen matrices to be deposited readily. A significant body of work therefore has focussed upon metal hydrides, dihydrogen complexes and other hydrogen species in matrices. Underpinning all of this experimental work are theoretical calculations, without which the correct identification of most matrix isolation molecules would remain dangerously ambiguous. Infrared spectroscopy remains-as it has for the past 50 years-the workhorse of matrix isolation studies. It does seem that this situation will not change-it is impossible to conceive of another spectroscopic method that combines the necessary sensitivity to study molecules at very low dilution with the structural information required to make a reasonably certain identification.

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Section: Groups 15-17mentioning

confidence: 99%

Chemistry in low-temperature matrices

Almond

Goldberg

2007

Annu. Rep. Prog. Chem., Sect. C: Phys. Chem.

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“…Other weak features were due to matrix-isolated CO, 15 F 2 CO, 16 FCOCl, 17 and Cl 2 CO 18 molecules, and to the OC••• ClF complex 19 also detectable in the initial FTIR spectrum of the OCSe/ClF/Ar matrix. These carbonyl-containing molecules can be formed in trace amount during the codeposition by thermal reaction between halogens and the CO liberated from OCSe.…”

Section: ■ Introductionmentioning

confidence: 98%

Photochemical Reaction of OCSe with ClF in Argon Matrix: A Light-Driven Formation of XC(O)SeY (X, Y = F or Cl) Species

et al. 2017

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The photochemistry of OCSe with ClF trapped together in argon matrices at cryogenic temperatures has been explored and the first interhalogen representatives of the elusive XC(O)SeY family, namely syn-ClC(O)SeF, anti-ClC(O)SeF, syn-FC(O)SeCl, and anti-FC(O)SeCl, as well as the hitherto triatomic species ClSeF complexed by a CO molecule, were obtained. Both ClC(O)SeF conformers appear to be produced independently by photolysis of the respective precursors; while formation of both FC(O)SeCl structures is ruled by the presence of an angular molecular complex OCSe···Cl-F formed prior to photolysis. This latter photochemical pathway seems to favor the formation of the less stable anti-FC(O)SeCl structure instead of the more stable syn- one. With the aid of quantum chemical calculations, using ab initio, DFT, TDDFT, and CASSCF methods, the mechanism for this photochemical reaction is rationalized both in terms of radical processes as well as a photoinduced electron transfer occurring into the OCSe···Cl-F complex. Also a singlet-triplet conical intersection between anti and syn rotamers of the FC(O)SeCl molecule is theoretically explored.

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“…For this molecule the most intense absorption bands appear at 1887, 1195, 1102 and 937 cm À1 , and are assigned to the n(CO), n as (CF 2 ), n s (CF 2 ) and n(CF), respectively. The compounds C(O)F 2 [14], C(O)FBr [15,16] and CF 3 OCF 2 C(O)F [17] were identified by their respective IR spectra. The bromotrifluoroethene epoxide, present in the reaction mixture, was characterized by its infrared band at 1540 cm À1 , assigned to the ring-breathing mode, that is characteristic of fluoroepoxides.…”

Section: Introductionmentioning

confidence: 99%

Formation of bromodifluoroacetyl fluoride, CF2BrC(O)F, in the thermal gas-phase oxidation of bromotrifluoroethene, CF2CFBr, initiated by trifluoromethylhypofluorite, CF3OF

Czarnowski

2006

Journal of Fluorine Chemistry

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The matrix-isolated molecular complexes CO/XF (X=Cl,Br,I) and the molecular structure of FC(O)Br

Cited by 7 publications

References 19 publications

Chemistry in low-temperature matrices

Chemistry in low-temperature matrices

Photochemical Reaction of OCSe with ClF in Argon Matrix: A Light-Driven Formation of XC(O)SeY (X, Y = F or Cl) Species

Formation of bromodifluoroacetyl fluoride, CF2BrC(O)F, in the thermal gas-phase oxidation of bromotrifluoroethene, CF2CFBr, initiated by trifluoromethylhypofluorite, CF3OF

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