Phosphinocyclopentadienid via Cyclopentadienylphosphid/ Phosphinocyclopentadienide via Cyclopentadienylphosphide

Abstract

Abstract 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 °C (R = Me) disproportionation is blocked and (PhP)4R- and (PhP)3R- can be detected. With excess RLi m onophosphides 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-l,2,3-triphospholene allylic anion.