Novel Ferrocene Derivatives with PH-Functionalized Phosphanylalkylcyclopentadienyl Ligands: Syntheses and Molecular Structures ofrac-[Fe{(η5-C5H4)CMe2PHR}2] (R = Ph, Mes) andrac-[Fe{(η5-C5H4)CMe2PHPh(Cp*TaCl4)}2]

Abstract

6,6‐Dimethylfulvene reacts with LiPHMes (Mes = 2,4,6‐Me3C6H2) to give Li[(C5H4)CMe2PHMes] (1). The ferrocene derivatives rac‐[Fe{(η5‐C5H4)CMe2PHR}2] [R = Ph (2), Mes (3)] are obtained in high yield from the lithium reagents Li[(C5H4)CMe2PHR] (R = Ph, Mes) and FeCl2. Compound 2 reacts with [Cp*TaCl4] to give the heterotrinuclear complex rac‐[Fe{(η5‐C5H4)CMe2PHPh(Cp*TaCl4)}2] (4). Compounds 1−4 were characterized spectroscopically, and crystal structure determinations were carried out on 2−4. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

Recent Advances in the Chemistry of Pentafulvenes

“…Lithium phosphides add to the exocyclic fulvene bond to provide phosphine substituted lithium Cp precursors for transmetalation onto Fe, 291,292 Cr, 293 Ti, 294−296 Zr, 294−296 and Nb 297 (Scheme 100). In one case, the intermediate phosphine adduct 352 initially yielded the transmetalation product 353, which then underwent reductive cleavage to furnish biscyclopentadienyl ansa complex 354.…”