Infrared spectroscopy and photochemistry of iron-ethylene oxide in cryogenic matrices. The FTIR spectrum of vinyl iron hydroxide
The mechanism of the cryogenic reaction between an iron atom and an ethylene oxide molecule has been delineated. Iron spontaneously inserted into the carbon-oxygen bond of the cyclic molecule and formed the first unligated metallaoxetane. Upon visible photolysis of ferraoxetane, a metathesis reaction was observed where cleavage occurred through the iron-carbon and the carbon-oxygen bonds of the metallacycle. UV photolysis of the reaction intermediate, an iron oxide ..pi..-complexed to ethylene, led to the activation of one of the C-H bonds of ethylene and the formation of the final product, vinyl iron hydroxide. Similar reaction pathways were observed for the diiron molecule reaction with ethylene oxide. Evidence for the double insertion of two iron atoms into the C-O bonds of ethylene oxide and the subsequent formation of a five-membered oxametallacycle ring has been seen through the detection of frequencies characteristic of an Fe-O-Fe stretching mode and a carbon-carbon stretching mode in the case of the perdeuterio product.
- Research Organization:
- Rice Univ., Houston, TX
- OSTI ID:
- 6336033
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 109:16
- Country of Publication:
- United States
- Language:
- English
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ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ETHERS
CHEMICAL PREPARATION
PHOTOLYSIS
ETHYLENE
CHEMICAL REACTIONS
HETEROCYCLIC OXYGEN COMPOUNDS
IRON
IRON COMPOUNDS
OXIDES
ABSORPTION SPECTROSCOPY
CARBON
CHEMICAL BONDS
CRYOGENICS
EXPERIMENTAL DATA
INFRARED SPECTRA
OXYGEN
PHOTOCHEMISTRY
REACTION INTERMEDIATES
ALKENES
CHALCOGENIDES
CHEMISTRY
DATA
DECOMPOSITION
ELEMENTS
HYDROCARBONS
INFORMATION
METALS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
SPECTRA
SPECTROSCOPY
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
400201* - Chemical & Physicochemical Properties
400500 - Photochemistry