Nature of odd-electron species and their role in catalytic processes. Progress report
ESR evidence is presented for the novel iron carbonyl radical anions Fe/sub 2/(CO)/sub 8//sup -/, Fe/sub 3/(CO)/sub 11/ and Fe/sub 4/(CO)/sub 13//sup -/. They are obtained either by alkali metal reduction of Fe(CO)/sub 5/ or by chemical oxidation of the corresponding carbonylate dianions in THF. The radical anion Fe/sub 3/(CO)/sub 12//sup -/ was also studied. /sup 57/Fe and /sup 13/C isotopic labelling studies greatly aided in the identification of these species as well as providing useful structural information. A novel series of radical anions, ((..pi..-olefin)Fe(CO)/sub 3/)/sup -/, have been prepared and spectroscopically characterized (ESR). With activated olefins, e.g., maleic anhydride, these species are obtained by reaction of the olefin with Na/sub 2/Fe(CO)/sub 4/ or by reduction of the (..pi..-olefin) Fe(CO)/sub 4/ complex with Na/K alloy or sodium napthalide in THF. A closely related series of iron carbonyl radical anions is obtained by similar reductions of (diene)Fe(CO)/sub 3/ complexes at low temperatures in THF/HMPA solutions. Isotopic labelling studies employing /sup 57/Fe and /sup 13/C were also carried out. 23 refs., 6 figs.
- Research Organization:
- Rutgers--the State Univ., Newark, NJ (USA). Dept. of Chemistry
- DOE Contract Number:
- AS05-80ER10662
- OSTI ID:
- 5866637
- Report Number(s):
- DOE/ER/10662-T2; ON: DE85010611
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
CARBON 13
CARBON ISOTOPES
CARBONYL RADICALS
CATALYTIC EFFECTS
DATA
ELECTRON SPIN RESONANCE
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
FURANS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
HYPERFINE STRUCTURE
INFORMATION
INTERMEDIATE MASS NUCLEI
IRON 57
IRON COMPOUNDS
IRON ISOTOPES
ISOTOPES
ISOTOPIC EXCHANGE
LABELLING
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RADICALS
RESONANCE
SPECTRA
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
TETRAHYDROFURAN
TRANSITION ELEMENT COMPOUNDS