om990377h_si_003.pdf (445.48 kB)
N,N‘-Diferrocenyl-N-heterocyclic Carbenes and Their Derivatives
journal contribution
posted on 1999-09-16, 00:00 authored by Benno Bildstein, Michael Malaun, Holger Kopacka, Klaus Wurst, Martin Mitterböck, Karl-Hans Ongania, Giuliana Opromolla, Piero ZanelloIn continuation of our work on Wanzlick/Arduengo carbenes containing redox-active
ferrocenyl substituents we report on the synthesis of N,N‘-diferrocenyl imidazol(in)ium salts
as precursors of imidazol(in)-2-ylidenes. The necessary starting material for this chemistry
is aminoferrocene, which was prepared by an improved and large-scale synthesis by the
sequence solid lithioferrocene, iodoferrocene, N-ferrocenylphthalimide, aminoferrocene. The
preparation of N,N‘-diferrocenyl heterocycles involves condensation of aminoferrocene with
glyoxal to afford N,N‘-diferrocenyldiazabutadiene [Fc-DAB], reduction, condensation with
formaldehyde, and oxidation with trityl salts to yield N,N‘-diferrocenylimidazol(in)ium salts.
In situ deprotonation and trapping with electrophiles yielded the expected metal complexes
and derivatives in some cases [Ag+ or S8], but attempted reaction with other transition metals
[e.g., Pd(II)] failed to give the corresponding complexes, due to (i) steric hindrance by the
two N-ferrocenyl substituents, (ii) reduced acidity of the imidazol(in)ium precursors, and
(iii) inaccessibility of the free carbenes. Spectroscopic [IR, Raman, UV−vis, MS, NMR (1H,
13C, 109Ag)], structural [X-ray], and electrochemical [CV] properties are reported and compared
to those of other N-heterocyclic carbene derivatives.