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Iron/alkene reactions: a matrix isolation infrared and Moessbauer investigation

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00162a010· OSTI ID:5581129
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The reactions of matrix-isolated iron atoms and clusters with the alkenes ethylene and propylene have been investigated by infrared and Moessbauer spectroscopies. In ethylene at low temperatures (<18 K) and with low iron concentrations (<1%) the major product is iron/ethylene comples (Fe(C/sub 2/H/sub 4/)). This is the only monoiron product formed, although unreacted iron atoms can be observed in pure ethylene at 4.2 K. Irradiation with the unfiltered output of a high-pressure Xe lamp causes the unreacted iron atoms to react to Fe(C/sub 2/H/sub 4/). At higher temperatures and iron concentrations additional products Fe/sub 2/(C/sub 2/H/sub 4/)/sub x/ (x = 1, 2) and Fe/sub p/(C/sub 2/H/sub 4/)/sub p/ (p > 2) are formed. Moessbauer spectra of iron/propylene complex (Fe/C/sub 3/H/sub 6/) at both 4.2 and 20 K are very similar to those of Fe/C/sub 2/H/sub 4/. Hence the products are similarly assigned to Fe(C/sub 3/H/sub 6/), Fe/sub 2/(C/sub 3/H/sub 6/)/sub 2/, and Fe/sub p/(C/sub 3/H/sub 6/)/sub p/ (p > 2). The Moessbauer spectra of the products indicate that the electronic configuration of the iron atoms in the alkene complexes is approximately (4s)/sup 1/(3d)/sup 7/, in agreement with theoretical work. The Moessbauer spectra of Fe(C/sub 2/H/sub 4/) and Fe(C/sub 3/H/sub 6/) are also consistent with the proposal that C/sub 2/H/sub 4/ and C/sub 3/H/sub 6/ are primarily sigma donors with only minimal d/sub ..pi../..--> pi..* back-bonding. 8 figures, 2 tables.
Research Organization:
Univ. of California, Santa Barbara
DOE Contract Number:
AM03-76SF00034
OSTI ID:
5581129
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 22:20; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical &amp; Physicochemical Properties
400301 -- Organic Chemistry-- Chemical &amp; Physicochemical Properties-- (-1987)
400500 -- Photochemistry
ALKALI METAL COMPOUNDS
ALKENES
ARGON
ATOMS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
COVER GAS
DATA
DEPOSITION
ELEMENTS
ENERGY-LEVEL TRANSITIONS
ETHYLENE
EVAPORATION
EVEN-ODD NUCLEI
EXCITATION
EXPERIMENTAL DATA
FLUIDS
GASES
HALIDES
HALOGEN COMPOUNDS
HELIUM
HYDROCARBONS
INERT ATMOSPHERE
INFORMATION
INFRARED SPECTRA
INTERMEDIATE MASS NUCLEI
IRON
IRON 57
IRON COMPLEXES
IRON ISOTOPES
ISOTOPE EFFECTS
ISOTOPE ENRICHED MATERIALS
ISOTOPES
LOW TEMPERATURE
MATERIALS
MATRIX ISOLATION
MATRIX MATERIALS
METALS
MOESSBAUER EFFECT
NONMETALS
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHASE TRANSFORMATIONS
POWDERS
PROPYLENE
RARE GASES
SODIUM CHLORIDES
SODIUM COMPOUNDS
SPECTRA
STABLE ISOTOPES
STOICHIOMETRY
STRUCTURAL CHEMICAL ANALYSIS
TEMPERATURE DEPENDENCE
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENTS
ULTRALOW TEMPERATURE
VERY HIGH TEMPERATURE
YIELDS