Migration Reaction of a Hypervalent Fragment: Base-Induced Migration of a Phosphorane Fragment from Iron to the Cyclopentadienyl Ring in Cp(CO)₂Fe{P(OC₆H₄Y)(OC₆H₄Z)} (Y, Z = NMe, NH, O)

Abstract

Iron phosphorane complexes, (Y, Z = NMe, O), react with lithium diisopropylamide (LDA) and then MeI to give showing the first example of migration of a hypervalent phosphorus fragment. The structure of one of the migration products, was determined by X-ray analysis. Spectroscopic monitoring of the migration reaction suggests that the reaction is initiated by a proton abstraction on the Cp ring by LDA, followed by migration of the phosphorane fragment to the Cp ring to give which is converted into by the treatment of alkyl halide. The reaction of containing two NH groups with LDA proceeds first with NH proton abstraction to give and then with Cp proton abstraction followed by phosphorane migration to give The addition of MeI finally led to the isolation of and

Phosphorane Migration from Ruthenium to the Cyclopentadienyl Ring

“…Therefore, Berry pseudorotation may be slower for complexes 2 , if it occurs at all, whereas it does occur faster for 4 than the NMR time scale. This tendency is the same as that exhibited by the corresponding iron complexes …”

“…(iv) In the IR spectrum, two absorption bands due to ν CO are observed at 2020 and 1959 cm -1 . These spectroscopic features are very similar to those for the corresponding iron complex …”

An unusually stable chlorophosphite: What makes BIFOP–Cl so robust against hydrolysis?

“…5 , Scheme 4 ). Hypervalent P(III)–O interactions with similar P–O distances are documented for five membered rings [ 47 – 48 ] as well as for acyclic systems [ 49 ].…”

Chiral Hypervalent, Pentacoordinated Phosphoranes

“…The reaction of the in situ generated anion 194a Moreover, it was found that in the presence of a base a migration of pentacoordinate phosphorane fragment occured from the transition metal in 196 to the carbon atom in the Cp ring in 201 [129] (Scheme 73). Moreover, it was found that in the presence of a base a migration of pentacoordinate phosphorane fragment occured from the transition metal in 196 to the carbon atom in the Cp ring in 201 [129] (Scheme 73). Moreover, it was found that in the presence of a base a migration of pentacoordinate phosphorane fragment occured from the transition metal in 196 to the carbon atom in the Cp ring in 201 [129] (Scheme 73).…”