Transition metal carbene complex

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A transition metal carbene complex in organometallic chemistry is a compound bearing a formal carbon-metal bond. The ligands coordinated to the metal center are carbenes. All transition metals are able to form these types of complexes. Many methods for synthesizing them and reactions utilizing them have been reported.

When the development of transition metal carbene complexes started in the mid-1970s, two different patterns of reactivity were discovered. At that time, these compounds were divided into two types. One of these types is called a Fischer Carbene named after Ernst Otto Fischer with strong π-acceptors at the metal. This complex is electrophilic at the carbene carbon atom which as considered in a singlet state. Following Arduengo's isolation of a stable free carbene in 1991, ^[1] a new field of transition metal complexes with N-heterocyclic carbenes (NHCs) has been opened.

1 Fisher carbenes
2 Schrock carbenes
3 N-heterocyclic carbenes
4 References
5 See also

[edit] Fisher carbenes

Fisher carbenes are found with :

low oxidation state metals
middle and late transition metals Fe(0), Mo(0), Cr(0)
pi electron acceptor metal ligands
pi-donor substituents on methylene group such as alkoxy and alkylated amino groups

The chemical bonding (scheme 1) is based on electron δ-type donation of the filled metal d-orbital to the empty p-orbital of the methylene group and pi electron back bonding of the filled methylene lone pair orbital to an empty metal d-orbital. An example is the complex (CO)₅Cr=C(NR₂)Ph.

[edit] Schrock carbenes

Schrock carbene, named after Richard R. Schrock do not have π-accepting ligands. This complex is nucleophilic at the carbene carbon atom in an unpaired triplet state.

Schrock carbenes are found with:

high oxidation states
early transition metals Ti(IV), Ta(V)
non pi-acceptor ligands
non pi-donor substituents

Bonding in this complex takes place when two methylene p-orbitals each containing a radical form two covalent bonds. These bonds are polarized towards carbon and therefore the methylene group is a nucleophile. An example of a Schrock carbene is the compound Cp₂(Me)Ta=CH₂ with a tantalum atom coordinated to a methylene group, a methyl group and two cyclopentadienyl groups. Another example is Tebbe's reagent.

Today, many carbene complexes bearing a broad range of different reactivities have been prepared. Often it is no longer possible to predict whether a carbene complex will behave as an electrophile or as a nucleophile. Thus, a reactivity-based nomenclature would be difficult to apply consistently.

[edit] N-heterocyclic carbenes

Typically, N-heterocyclic carbenes are good σ-donors but poor π-acceptors. Due to the poor π-backbonding in NHC-metal complexes, the bond between the carbon and the metal center is usually formally represented by a single bond compared with Fischer and Schrock carbenes.

In catalytic studies, NHCs are often compared with well-established phosphine-based complexes. The advantages of NHCs over phosphines include the lack of toxicity compared with phosphines and the ease of handling.

[edit] References

↑ A. J. Arduengo III, R. L. Harlow, M. Kline, J. Am. Chem. Soc., 1991, 113, 361.
The Organometallic Chemistry of the Transition Metals R.H. Crabtree ISBN 0-471-85306-2