HANDOUT 2

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:

If we look at this from a molecular/atomic orbital perspective, one lone pair is

donated from the singlet carbene to an empty d-orbital on the metal (red), and a
lone pair is back-donated from a filled metal orbital into a vacant pz orbital on
carbon (blue). There is competition for this vacant orbital by the lone pair(s) on
the heteroatom, consistent with our second resonance structure. Overall, the
bonding closely resembles that of carbon monoxide. Therefore, carbene ligands
are usually thought of as neutral species, unlike dianionic Schrock alkylidenes
(which usually lack electrons for back-donation). But remember that electron
counting is just a formalism!
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The stabilization of a partial positive charge on the carbene ligand has predictable
consequences that show up in the reactivity and spectroscopic features (see
below).

Structural and Spectroscopic Features

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.
1. From metal carbonyls. This is the most common method:

2. Activation of a neutral acyl complex:

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3. Rearrangement of coordinated ligands. The tautomerization of terminal alkyne

complexes to acetylides is well known. Transfer of the hydride to the beta-carbon
affords a vinylidene:

Acetylides can be easily synthesized from Li or SiMe3 acetylides. These species

are quite reactive towards electrophiles at the beta carbon, i.e. they are easily
protonated or alkylated:

4. From activated olefins (very strained or electron-rich). This methodology was

used by Grubbs to synthesize olefin metathesis catalysts:

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Reactivity
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):

2. Olefin metathesis. While some Fischer carbenes are excellent metathesis

catalysts, they are rarely energetically favorable. More commonly, reaction with
olefins results in cyclopropanation (next item).
3. Cyclopropanation. The intermediate metallacyclobutane that is formed from the
[2 + 2] cycloaddition of an olefin to a carbene can decompose in several different
ways. A retro [2 + 2] can lead to olefin metathesis. However, the metallacycle can
also decompose with the formation of a cyclopropane (Casey et. al. J. Am Chem.
Soc. 1976, 98, 608).

These reactions go in good yield and are stereospecific. A second example is by

Helquist et al. J. Am. Chem. Soc. 1982, 104, 1869:

Substituting a phosphine for one CO in the above reaction leads to good

enantiomeric excess. One should note that there is well-developed

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cyclopropanation chemistry using diazoalkanes (explosive!) as the carbene

source; organometallic reagents are much safer.
4. The Dtz Reaction. A phenyl-substituted carbene, alkyne and carbon monoxide
are converted into substituted naphthols!

The metal can be easily cleaved from the naphthol. Dtz-type chemistry is welldeveloped 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.

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