78897-25-3Relevant articles and documents
Is π-back-bonding important for σ-bound aldehyde and ketone complexes? Synthesis and structural characterization of aromatic aldehyde complexes of the [CpFe(CO)2]+ cation
Cicero, Ronald L.,Protasiewicz, John D.
, p. 4792 - 4798 (2008/10/09)
The synthesis and characterization of a series of organometallic complexes, [CpFe(CO)2-(O=C(H)Ar)]PF6 (Ar = Ph (1), p-MeC6H4 (2), p-NMe2C6H4 (3), p-OMeC6H4 (4), p-CF3C6H4 (5), p-ClC6H4 (6), p-(dimethylamino)cinnamaldehyde (7); Cp = η5-cyclopentadienyl) are presented. Oxidation of [CpFe(CO)2]2 with AgPF6 or [Cp2Fe]PF6 in the presence of a 5-fold excess of aromatic aldehyde led to the formation of 1-7 in good to excellent yields (especially with the latter oxidant). Compounds 1-7 were analyzed by a combination of 1H NMR (solution) and FTIR spectroscopic (solid and solution state) methods. Single-crystal X-ray diffraction studies on 6 and [CpFe(CO)2(O=C(H)-p-OMeC6H4)]SbF6 (8) were also performed. Binding of these aldehydes to [CpFe(CO)2]+ in solution and the solid state occurs exclusively through oxygen π-donor interactions. Structural evidence for π-back-bonding in σ-bound aldehyde complexes is presented. These solid-state effects, however, do not manifest themselves in the solution equilibrium binding constants for this class of substrates.