Defluorination of perfluoroolefins by divalent lanthanoid reagents: Activating C-F bonds
- E.I. du Pont de Nemours and Co., Wilmington, DE (USA)
Divalent lanthanoid complexes MCp*{sub 2} {times} L (M = Yb, Eu, Sm; L = diethyl ether or THF; Cp* = {eta}{sup 5}-pentamethylcyclopetadienyl) and YbCp{prime}{sub 2} {times} L (Cp{prime} = {eta}{sup 5}-methylcyclopentadienyl; L = tetrahydrofuran) rapidly abstract fluorine atoms from a variety of perfluoroolefins including perfluoro-2,4-dimethyl-3-ethylpent-2-ene, perfluoro-2,3-dimethylpent-2-ene, and perfluorocyclohexene. Qualitative observation shows that the relative fluorine abstraction reactivity of the four lanthanoid complexes increases with increasingly negative reduction potential for reasonably unhindered fluoroolefin substrates. The Yb(III)/Yb(II) reduction potential of YbCp{prime}{sub 2} solvated in acetonitrile is determined here to be {minus}1.65 V (relative to ferrocene) by cyclic voltammetry. The fully characterized organometallic products from the fluorine atom abstraction reactions are solvated trivalent lanthanoid fluorides MCp*{sub 2}F {times} L (M = Yb, Eu, Sm; L = diethyl ether or THF) and YbCp{prime}{sub 2}F {times} THF. The molecular structures of YbCp*{sub 2}F {times} OEt{sub 2} and YbCp*{sub 2}F {times} THF determined by X-ray crystallography reveal the first terminal lanthanoid-fluoride bonds.
- OSTI ID:
- 6379656
- Journal Information:
- Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:7; ISSN 0276-7333; ISSN ORGND
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTIONS
COMPLEXES
DATA
DATA ANALYSIS
DEHALOGENATION
EUROPIUM COMPLEXES
EXPERIMENTAL DATA
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RARE EARTH COMPLEXES
REAGENTS
SAMARIUM COMPLEXES
YTTERBIUM COMPLEXES