- Phosphorus-carbon bond forming reactions of iron tetracarbonyl-coordinated phosphenium ions
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Abstraction of chloride from [Fe(CO)4(PPh2Cl)] (1) in the presence of PPh3 leads to [Fe(CO)4(PPh2(PPh3))][AlCl4] (2), an iron complex of a phosphine-coordinated phosphenium ion. The PPh3 is readily displaced by ferrocene, leading to an electrophilic aromatic substitution reaction, and formation of [Fe(CO)4{PPh2Fc}] (3) (Fc = ferrocenyl). Alternately, chloride abstraction from 1 in the presence of ferrocene leads directly to 3, via a transient phosphenium ion complex. The transient phosphenium ion complex also reacts with N,N-diethylaniline, indole, and pyrrole to form the respective p-anilinyl, 3-indolyl, and 2-pyrryl phosphine complexes via electrophilic aromatic substitution. Chloride abstraction from [Fe(CO)4(PPhCl2)] in the presence of ferrocene leads to a double substitution reaction, forming [Fe(CO)4{PPhFc2}] (13).
- King, Ryan C.,Nilewar, Shrikant,Sterenberg, Brian T.
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- DIHALOGENPHOSPHANCOMPLEXE ALS METALLORGANISHE SYNTHESEBAUSTEINE
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The dichlorophosphanes (R)P(Cl)2 react with Fe2(CO)9 to give (CO)4Fe-P(R)(Cl)2 (I) in high yields.When treated with Fe2(CO)9 in 2.5 M excess, compounds I give the μ2-chloro-μ2-chlorophosphido-bridged dinuclear molecules II, Fe2(CO)6(μ2-Cl)(μ2-PRCl).Further treatment of II with Fe2(CO)9 resulsts in the formation of the trinuclear clusters IV, Fe3(CO)10(μ3-PR).Zinc reduction of II leads to V, Fe4(CO)11)(μ4-PR)2.All of these reactions lead to fairly high yields for a variety of substituents R.The product selectivity is effectively controlled by the stoichiometry.The syntheses and properties of the main products I,II,IV and V, as well as those of the dinuclear side-products 2-PRCl)>2 (III), 2-PRCl)>2 (VI), and the trinuclear species (CO)9Fe3(μ3-PR)2 (VII), are discussed.
- Lang, Heinrich,Zsolnai, Laszlo,Huttner, Gottfried
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