- Formation of a cationic alkylidene complex via formal hydride abstraction: Synthesis and structural characterization of [W(PMe3) 4(η2-CHPMe2)H]X (X = Br, I)
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W(PMe3)4(η2-CH2PMe 2)H reacts with aryl halides to give the alkylidene complex, [W(PMe3)4(η2-CHPMe2)H] +, which reacts with LiAlD4 to give selectively W(PMe 3)4(η2-CHDPMe2)H, in which the deuterium resides in the methylene group; subsequent migration of deuterium from the methylene group provides a means to measure the rate constant for the formation of the 16-electron species [W(PMe3)5] from W(PMe3)4(η2-CH2PMe 2)H.
- Sattler, Aaron,Parkin, Gerard
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supporting information; experimental part
p. 12828 - 12830
(2012/01/13)
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- Phosphinocyclopentadienide via Cyclopentadienylphosphide
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Lithiumorganyls RLi (R = Me, Bu, Ph) add to (PhP)5 in successive degradation and disproportionation equilibria depending on the ratio of the reactants.At -70 deg C (R = Me) disproportionation is blocked and (PhP)4R(-) and (PhP)3R(-) can be detected.With excess RLi monophosphides PhPR(-) are formed.CpNa with the help of a crown ether degrades (PhP)5 or substitutes cyanide from PhPCN(-) to give an equilibrium mixture of (PhP)nCp(-) anions, which stabilize by proton shifts: In case of n = 1 and 2 a shift from the Cp unit to the terminal phosphorus results in the formation of the phenylphosphino- and diphenyldiphosphino-cyclopentadienide anion, in case of n = 3 two proton shifts within the Cp unit result in a cyclopenteno-1,2,3-triphospholene allylic anion. - Keywords: Cyclophosphane, Cyclopentadienide, Nucleophilic Degradation, 31P NMR Spectra
- Schmidpeter, Alfred,Zirzow, Karl-Heinz
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p. 977 - 983
(2007/10/02)
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