Infrared spectroscopy and photochemistry of iron-ethylene oxide in cryogenic matrices. The FTIR spectrum of vinyl iron hydroxide
Abstract
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.
- Authors:
- Publication Date:
- Research Org.:
- Rice Univ., Houston, TX
- OSTI Identifier:
- 6336033
- Resource Type:
- Journal Article
- Journal Name:
- J. Am. Chem. Soc.; (United States)
- Additional Journal Information:
- Journal Volume: 109:16
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, 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
Citation Formats
Kafafi, Z H, Hauge, R H, Billups, W E, and Margrave, J L. Infrared spectroscopy and photochemistry of iron-ethylene oxide in cryogenic matrices. The FTIR spectrum of vinyl iron hydroxide. United States: N. p., 1987.
Web. doi:10.1021/ja00250a003.
Kafafi, Z H, Hauge, R H, Billups, W E, & Margrave, J L. Infrared spectroscopy and photochemistry of iron-ethylene oxide in cryogenic matrices. The FTIR spectrum of vinyl iron hydroxide. United States. https://doi.org/10.1021/ja00250a003
Kafafi, Z H, Hauge, R H, Billups, W E, and Margrave, J L. 1987.
"Infrared spectroscopy and photochemistry of iron-ethylene oxide in cryogenic matrices. The FTIR spectrum of vinyl iron hydroxide". United States. https://doi.org/10.1021/ja00250a003.
@article{osti_6336033,
title = {Infrared spectroscopy and photochemistry of iron-ethylene oxide in cryogenic matrices. The FTIR spectrum of vinyl iron hydroxide},
author = {Kafafi, Z H and Hauge, R H and Billups, W E and Margrave, J L},
abstractNote = {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.},
doi = {10.1021/ja00250a003},
url = {https://www.osti.gov/biblio/6336033},
journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 109:16,
place = {United States},
year = {Wed Aug 05 00:00:00 EDT 1987},
month = {Wed Aug 05 00:00:00 EDT 1987}
}