Reductive defluorination of saturated fluorocarbons by organometallic reagents and aryl halide coordination to tungsten(II) and molybdenum(II) by chelating Schiff base ligands
Strong organometallic nucleophiles cleave C-F bonds of fluorocarbons such as perfluorodecalin and perfluoro(methylcyclohexane) to afford complexes of the form Cp(CO)[sub 2]FeR, where R is a fluoro aromatic derivative of the perfluorocarbon, when NaCpFe(CO)[sub 2] is used as a nucleophile. Fluoride ion and [Cp(CO)[sub 2]Fe][sub 2] are also recovered in good yields. The reaction occurs at ambient temperature and reaction times vary from one to four hours depending on the substrate used. An electron transfer mechanism is proposed and radical character exists in the intermediates, as evident by hydrogen incorporation into the fluorocarbon products and rate enhancement when the reaction is run in the presence of a hydrogen radical donor. The reactivity patterns of model systems indicate hydrogen incorporation occurred early along the reaction pathway. NaRe(CO)[sub 5] and Ni(P(C[sub 2]H[sub 5])[sub 3])[sub 4] also show reactivity towards the perfluorosubstrates, but NaCpMo(CO)[sub 3] and Na[sub 2]Fe(CO)[sub 4] do not. Aryl-X (X = Cl, Br, I, OCH[sub 3]) groups coordinate to Mo(II) and W(II), through the lone pairs on the atoms, forming seven coordinate metal carbonyls, when chelating nitrogen Schiff base ligands are oxidatively added to W(CO)[sub 3](NCCH[sub 3])[sub 3] or Mo(CO)[sub 3](toluene) in THF. The major mode of reactivity of these coordination compounds is aryl halide dissociation. Competition with typical solvents as monitored by solution IR and ligand equilibrium studies give relative bond strengths. X-ray crystallography shows covalent bonding between the metal and aryl halide groups and the metal geometry is capped octahedral. The aryl halide complexes substitute CO preferentially over the aryl halide when exposed to phosphine donor ligands. Aryl-fluoride coordination was not detected, but halide bridged metal dimers were isolated instead.
- Research Organization:
- Utah Univ., Salt Lake City, UT (United States)
- OSTI ID:
- 6914613
- Resource Relation:
- Other Information: Thesis (Ph.D.)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
MOLYBDENUM COMPLEXES
CHEMICAL REACTIONS
ORGANIC FLUORINE COMPOUNDS
ELECTRON TRANSFER
FLUORINATION
REDUCTION
TUNGSTEN COMPLEXES
ARYLATION
CHELATES
COORDINATION NUMBER
ORGANOMETALLIC COMPOUNDS
SCHIFF BASES
COMPLEXES
HALOGENATION
IMINES
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
TRANSITION ELEMENT COMPLEXES
400400* - Electrochemistry