ESR spectra and structure of the perchloryl fluoride radical anion (FC1O/sub 3//sup -/): A 33 valence electron radical with C/sub 30/ symmetry

Journal Article · Tue Dec 01 23:00:00 EST 1981 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00414a003· OSTI ID:5735294

Hasegawa, A; Williams, F

The isotropic and anisotropic ESR spectra of FClO/sub 3//sup -/ have been observed, the former in the SF/sub 6/ matrix and the latter in both the FClO/sub 3/ and (CH/sub 3/)/sub 4/Si matrices. The isotropic hyperfine coupling constants derived from the anisotropic parameters agree with the values (/sup 35/a = 656 MHz, /sup 37/a = 546 MHz, /sup 19/a = 726 MHz) obtained from the isotropic spectrum. Moreover, the analysis of the anisotropic spectrum reveals that the chlorine and fluorine hyperfine tensors have cylindrical symmetry with their largest principal values lying along the same principal axis. This result rules out a trigonal-bipyramidal structure for this 33 valence electron radical but is entirely consistent with a C/sub 3/V structure in which the Cl-F bond represents the symmetry axis (z). Most of the spin density is concentrated in the antibonding sigma/sub Cl-F/* orbital which is composed of the 3s and 3p/sub z/ orbitals of chlorine (p/sub 3s/ = 0.14, p/sub 3p/ = 0.40) in combination with the 2p/sub z/ orbital of fluorine (p = 0.35). These results are in qualitative agreement with CNDO/2 calculations which also show that the Cl-F bond is longer in the radical anion than in the parent molecule. As expected from a consideration of its electronic structure, FClO/sub 3//sup -/ dissociates to give the neutral ClO/sub 3/ radical which has been detected in the SF/sub 6/ matrix.

• Research Organization: Univ. of Tennessee, Knoxville
• OSTI ID: 5735294
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:24; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ANIONS
ANISOTROPY
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
CHLORINE 35
CHLORINE 37
CHLORINE COMPOUNDS
CHLORINE ISOTOPES
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
FLUORIDES
FLUORINE 19
FLUORINE COMPOUNDS
FLUORINE ISOTOPES
GAMMA RADIATION
HALIDES
HALOGEN COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
HYPERFINE STRUCTURE
INFORMATION
IONIZING RADIATIONS
IONS
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
OXYGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADICALS
RADIOLYSIS
RESONANCE
SILANES
SILICON COMPOUNDS
STABLE ISOTOPES
SULFUR COMPOUNDS
SULFUR FLUORIDES