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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.
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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 p-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, a new field of transition metal complexes with N-heterocyclic carbenes (NHCs) has been opened.
Fischer carbenes
Fischer carbenes are found with :
The chemical bonding (scheme 1) is based on electron d-type donation group of the filled methylene lone pair orbital to an empty metal d-orbital, and pi electron back bonding of the filled metal d-orbital to the empty p-orbital of the methylene. An example is the complex (CO)5Cr=C(NR2)Ph.
Fischer carbenes can be likened to ketones, with the carbene carbon being electrophilic, much like the carbonyl carbon of a ketone. Like ketones, Fischer carbene species can undergo Aldol-like reactions. The hydrogen atoms attached to the carbon α to the carbene carbon are acidic, and can be deprotonated by a base such as n-butyllithium, to give a nucleophile which can undergo further reaction.
This carbene is also the starting material for other reactions such as the Wulff-Dötz reaction. These type of carbenes were discovered by E. O. Fischer, and together with other achievements in organometalic chemistry, he was awarded the Nobel prize.
Schrock carbenes
Schrock carbenes, named after Richard R. Schrock, do not have p-accepting ligands. This complex is nucleophilic at the carbene carbon atom in an unpaired triplet state.
Schrock carbenes are found with:
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.
N-heterocyclic carbenes
Typically, N-heterocyclic carbenes are good s-donors but poor p-acceptors. Due to the poor p-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.
See also
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