ESR study of x-irradiated (HP(OCH/sub 2/CH/sub 2/)/sub 3/N)BF/sub 4/: Phosphorus in a trigonal-bipyramidal configuration with the unpaired electron in apical position
The single crystal study of the radical derived from x-irradiated (HP(OCH/sub 2/CH/sub 2/)/sub 3/N)BF/sub 4/ (1) is reported here. X-ray crystallography studies show that the phosphorus atom possesses a trigonal bipyramidal (TBP) structure with the adjacent hydrogen and nitrogen atoms in the apical positions. The ESR spectra of an x-irradiated single crystal of 1 show that two identical radicals with an angle between their apical position components of 90 +- 2/sup 0/ are present on rotation about the crystallographic c axis. The occurrence of differently oriented radicals is consistent with the x-ray analysis of precursor 1, which also shows two orientations in the unit cell. However, in the latter case, the angles between the P-N linkages are 66/sup 0/. Taking into account that two such molecules are mirror images, the structure of 2 can be described as a slightly deformed TBP configuration in which the unpaired electron and the nitrogen atom occupy the apical sites.
- Research Organization:
- Eindhoven Univ. of Technology, Netherlands
- OSTI ID:
- 6840891
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 102:17
- Country of Publication:
- United States
- Language:
- English
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BORON FLUORIDES
RADIOLYSIS
ORGANIC NITROGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
RADICALS
ELECTRON SPIN RESONANCE
ELECTRONIC STRUCTURE
X RADIATION
X-RAY DIFFRACTION
BORON COMPOUNDS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
COHERENT SCATTERING
DECOMPOSITION
DIFFRACTION
ELECTROMAGNETIC RADIATION
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
IONIZING RADIATIONS
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RESONANCE
SCATTERING
400600* - Radiation Chemistry