Abstract

DIAZ, C.; CABEZAS, N.  and  MENDIZABAL, F.. NEW ENTRY TO PIANO -STOOL ELECTRON RICH (PENTAMETHYL CYCLOPENTADIENYL) IRON COMPLEXES. Bol. Soc. Chil. Quím. [online]. 2002, vol.47, n.3, pp.213-220. ISSN 0366-1644.  http://dx.doi.org/10.4067/S0366-16442002000300003.

A new route to the electron rich pentamethylcyclopetadienyl iron complexes (n⁵-C₅Me₅)=Cp*) starting from the commercially available dimer [Cp*Fe(CO)₂]₂ ,is presented. Reaction of the dimer with I₂ in CH₂Cl_2, affords the mononuclear carbonyl complex Cp*Fe(CO)₂I which in turn reacts with bis(diphenylphosphinoethane) in toluene under Uv irradiation to give Cp*Fe(dppe)I. Treatment of Cp*Fe(dppe)I with the neutral ligands L (L = CH₃CN, PPh₃, SEt₂) in the presence of TlPF₆ affords the cationic derivatives [Cp*Fe(dppe)L]PF₆ ,while that the reaction with S₂(CH₂C₆H₅ )₂ in CH₃OH yields the thiolate complex [Cp*Fe(dppe)S-CH₂C₆H₅ ] PF₆ .The unusual magnetic properties of these complexes are discussed. Extended Hückel OM calculation confirmed the most electron rich character of the Cp*Fe(dppe)⁺ derivatives than their unsustituted CpFe(dppe)⁺ .Electrochemical as well as Mösbauer data are in agree with this

Keywords : pentamethylcyclopentadienyl iron; electron rich fragments; OM calculation; organometallic.