Photosensitized reaction of /sup 3/P Hg, Cd, and Zn atoms with diffuorochloroethene in krypton matrix
The reaction between M(/sup 3/P) atoms (M = Hg, Cd, Zn) with difluorochloroethene (CDFE) and deuteriodifluorochloroethene (CDFE-d) in krypton matrix at 12 K has been studied. The usual gas-phase reaction caused by mercury-photosensitization of halogenated ethenes, elimination of HX (or H/sub 2/), is not observed. Instead, each of these class IIB (group 12 in the new notation) metal atoms gives a reaction product with an absorption spectrum that resembles that of the parent olefin but shifted significantly to lower frequencies. For mercury, the product is identified as 1,1-difuorovinylmercuric chloride, (F/sub 2/C=CH) HgCl, the net result of mercury insertion into the carbon chlorine bond. Cadmium and zinc apparently give analogous products. The preferential insertion into the C-Cl bond indicates that reaction is constrained in krypton matrix to a triplet reaction surface and suggests that there is an activation energy barrier connected with the change in shape of the olefin in its planar, ground state to the twisted triplet state. The reactivity of the Hg(/sup 3/P) state relative to that of the ground state is attributed to its partially occupied valence orbitals. In view of the infrared spectrum of CDFE-d, the vibrational assignment deduced earlier for CDFE must be altered. 21 references, 4 figures, 4 tables.
- Research Organization:
- Univ. of California, Berkeley
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 6962031
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 90:9
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CADMIUM
PHOTOCHEMISTRY
DEUTERIUM COMPOUNDS
ETHYLENE
MERCURY
ORGANIC CHLORINE COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ZINC
ABSORPTION SPECTROSCOPY
EXPERIMENTAL DATA
INFRARED SPECTRA
ISOTOPE EFFECTS
KRYPTON
LABELLING
MATRIX ISOLATION
ULTRALOW TEMPERATURE
ALKENES
CHEMISTRY
DATA
ELEMENTS
FLUIDS
GASES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
METALS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RARE GASES
SPECTRA
SPECTROSCOPY
400500* - Photochemistry