Contribution a l'etude des metallocenes—XXIII

New, Simple Synthetic Route to Functional Mono- and Biferrocenes

“…The complexes [(η 5 -C 5 H 5 )Fe(η 6 -toluene)][PF 6 ], Na[η 5 -C 5 H 4 COCH 3 ], Na[η 5 -C 5 H 4 CO 2 CH 3 ], Na 2 [1,4-C 6 H 4 (CH 2 C 5 H 4 ) 2 ], Li[η 5 -C 5 H 4 P(C 6 H 5 ) 2 ], Li[η 5 -C 5 H 4 Si(CH 3 ) 2 CH 2 Cl], [(η 5 -C 5 H 4 CO 2 H)Fe(η 6 -toluene)][PF 6 ], [(η 5 -C 5 H 4 COCl)Fe(η 6 -toluene)][PF 6 ], [(η 5 -C 5 H 4 COMe)Fe(η 6 -toluene)][PF 6 ], [(η 5 -C 5 H 4 Cl)Fe(η 6 -toluene)][PF 6 ], [Fe 2 Fv(η 5 -C 5 H 5 ) 2 ] (Fv = μ 2 -η 5 , η′ 5 -fulvalenediyl), [(η 5 -C 5 H 4 Me)Fe(η 6 -toluene)][PF 6 ], and [(η 5 -Cp*)Fe(η 6 -toluene)][PF 6 ] were synthesized according to the references.…”

“…They are are robust, being stable thermally up to above 200 °C. The parent complex [CpFe(η 6 -C 6 H 6 )][PF 6 ] and many derivatives are stable in concentrated sulfuric acid . These families have a very rich ring-functionalization chemistry for both the Cp and arene ligands, and their redox chemistry is well-known with reversibility properties .…”

Ligand Exchange Reaction of Ferrocene with Heterocycles

“…Therefore, these hetero atoms would produce a decrease in the π-electron density and deviation on the benzene ring. These would decrease the ability to coordinate as the η 5 -ligand. The sulfur analogue, benzothiophene, gave the exchange product as well as the carbon analogue, indene, because of the lower electronegativity of the sulfur atom.…”

“…This reaction is initiated by pulling the Cp ring by AlCl 3 in the vertical direction, so that the ferrocene decomposes into two fragments. The resulting fragment containing an iron atom is coordinated by an aromatic ring (Scheme 2) [4] [5].…”

Molecular motion in solids: Mössbauer spectra of [Fe(η-C6H6)(η-C5H5)][AsF6]

“…Since the first preparation and characterization of the mixed sandwich cationic compound [Fe(q-c,H,)(q-C,H,)] +, many further examples have been prepared, their physical and chemical properties investigated 2 . 3 and several crystal and molecular structures determir~ed.~ We have reported on the large-amplitude reorientational motion that is active in the crystalline hexafluorophosphate la. 5 This reorientational motion corresponds to rotations in the xy, zx or zy planes of the crystal and as such is readily detected with the aid of Mossbauer spectroscopy if and when the reorientational rate is close to the reciprocal of the quadrupole precession time.…”