6002-62-6Relevant academic research and scientific papers
Phosphinocyclopentadienide via Cyclopentadienylphosphide
Schmidpeter, Alfred,Zirzow, Karl-Heinz
, p. 977 - 983 (2007/10/02)
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
On Organophosphorus Compounds, XXII. 1,2-Diaryl-1,2-dibromodiphosphanes
Hinke, Axel,Kuchen, Wilhelm
, p. 3003 - 3010 (2007/10/02)
1,2-Diaryl-1,2-dibromodiphosphanes R(Br)P-P(Br)R 2 (R = C6H5; 4-XC6H4, X = CH3O, F, Cl) were prepared by dehalogenation of RPBr2 with magnesium in a one-batch procedure.While solid 2 presumably consists of only one diastereomer there exists an equilibrium between meso-2, rac-2 and their disproportionation products RPBr2 and (RP)5 in solutions of 2.The influence of temperature, R and solvent on this equilibrium was investigated. - The reaction products of the dissolved phenyl compound 2a correspond to a reaction of its disproportionation products PhPBr2 and (PhP)5, the former preferably reacting on nucleophilic substitution, the latter with electrophilic agents.Under heterogenous conditions diphosphanes Ph(R)P-P(R)Ph can be obtained from 2a and LiR.
