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Handout2 Fischer Carbene
Handout2 Fischer Carbene
Fischer Carbene
General Information
Carbene ligands possess a metal-carbon double bond and are closely related to
alkylidenes. Carbene ligands (B) have a heteroatom substituent unlike alkylidenes
(A) which usually have alkyl substituents on the alpha carbon atom:
These are sometimes called Fischer carbenes in honor of E.O. Fischer, who
reported the first example in 1964 and later won a Nobel Prize for his pioneering
work on ferrocene with Wilkinson.
Fischer carbenes are typically found on electron-rich, low oxidation state metal
complexes (mid to late transition metals) containing pi-acceptor ligands. The
presence of the heteroatom on the alpha carbon allows us to draw a resonance
structure that is not possible for an unsubstituted (Schrock-type) alkylidene:
Single crystal x-ray diffraction studies confirm that the second resonance form
shown above plays a major role in describing the bonding in metal carbene
complexes. The metal double carbon bonds in these complexes tend to be longer
than typical M=C double bonds, but shorter than M-C single bonds. Likewise, the
carbon-heteroatom bond length is somewhat shorter than a typical M-E bond. For
example, in the case below, a "normal" C-N bond is 145 pm:
The stronger the pi-donor on the carbene carbon, the lower the M=C bond order
and lower the barrier to rotation around the M-C bond.
Proton and carbon NMR data are similar to those observed for alkylidene
complexes, however, Fischer carbenes do not typically display any unusual JCH
values that might indicate an agostic interaction between the carbene proton and
the metal.
Fischer carbenes often contain carbonyl ligands which can provide very useful
NMR and IR data.
Synthesis
There are many synthetic methods for the synthesis of carbene complexes. The four most
common ones are shown here.
Fischer carbenes exhibit such a wide manifold of reactivity, that an entire text could be
devoted to them. Some of the more common reaction pathways are shown here.
1. Heteroatom substitution. The electrophilic nature of the C atom in Fischer
carbenes means the heteroatom can often be exchanged by simple nucleophilic
displacement (Casey, C. P.; Shusterman, A. J. J. Mol. Catal. 1980, 8, 1):
The metal can be easily cleaved from the naphthol. Dötz-type chemistry is well-
developed and has been used to prepare Vitamin E as well as some antibiotics.
What is the mechanism of this "termolecular" reaction? Experiments show that
the rate is inhibited by excess CO or phosphine, so the first step must be
dissociation of CO. Coordination of the alkyne, formation of a
metallacyclobutene, insertion of CO into the ring, rearrangement to a pi-complex,
ring closure and a proton shift account for our observed product (whew!):
5. Many more! Fischer carbene complexes undergo many other kinds of annulation
reactions, Diels-Alder reactions etc.