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Transition metal carbene complex
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Transition metal carbene complex
A transition metal carbene complex is an organometallic compound featuring a divalent carbon ligand, itself also called a carbene. Carbene complexes have been synthesized from most transition metals and f-block metals, using many different synthetic routes such as nucleophilic addition and alpha-hydrogen abstraction. The term carbene ligand is a formalism since many are not directly derived from carbenes and most are much less reactive than lone carbenes. Described often as =CR2, carbene ligands are intermediate between alkyls (−CR3) and carbynes (≡CR). Many different carbene-based reagents such as Tebbe's reagent are used in synthesis. They also feature in catalytic reactions, especially alkene metathesis, and are of value in both industrial heterogeneous and in homogeneous catalysis for laboratory- and industrial-scale preparation of fine chemicals.
Metal carbene complexes are often classified into two types. The Fischer carbenes, named after Ernst Otto Fischer, feature strong π-acceptors at the metal and are electrophilic at the carbene carbon atom. Schrock carbenes, named after Richard R. Schrock, are characterized by more nucleophilic carbene carbon centers; these species typically feature higher oxidation state (valency) metals. N-Heterocyclic carbenes (NHCs) were popularized following Arduengo's isolation of a stable free carbene in 1991. Reflecting the growth of the area, carbene complexes are now known with a broad range of different reactivities and diverse substituents. Often it is not possible to classify a carbene complex solely with regards to its electrophilicity or nucleophilicity.
The common features of Fischer carbenes are:
Examples include (CO)5W=COMePh and (OC)5Cr=C(NR2)Ph.
Fischer carbene complexes are related to the singlet form of carbenes, where both electrons occupy the same sp2 orbital at the carbon. This lone pair donates to a metal-based empty d orbital, forming a σ bond. π-backbonding from a filled metal d orbital to the empty p orbital of the carbon atom is possible. However this interaction is generally weak since the alpha donor atoms also donate to this orbital. As such, Fischer carbenes are characterized as having partial double bond character. The major resonance structures of Fischer carbenes put the negative charge on the metal centre, and the positive on the carbon atom, making it electrophilic.
Fischer carbenes can be likened to ketones, with the carbene carbon atom being electrophilic, like the carbonyl carbon atom of a ketone. This can be seen from the resonance structures, where there is a significant contribution from the structure bearing a positive carbon centre. Like ketones, Fischer carbene species can undergo aldol-like reactions. The hydrogen atoms attached to the carbon atom α to the carbene carbon atom are acidic, and can be deprotonated by a base such as n-butyllithium, to give a nucleophile, which can undergo further reaction.
Schrock carbenes do not have π-accepting ligands on the metal centre. They are often called alkylidene complexes. Typically this subset of carbene complexes are found with:
Examples include ((CH3)3CCH2)Ta=CHC(CH3)3 and Os(PPh3)2(NO)Cl(=CH2).
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Transition metal carbene complex
A transition metal carbene complex is an organometallic compound featuring a divalent carbon ligand, itself also called a carbene. Carbene complexes have been synthesized from most transition metals and f-block metals, using many different synthetic routes such as nucleophilic addition and alpha-hydrogen abstraction. The term carbene ligand is a formalism since many are not directly derived from carbenes and most are much less reactive than lone carbenes. Described often as =CR2, carbene ligands are intermediate between alkyls (−CR3) and carbynes (≡CR). Many different carbene-based reagents such as Tebbe's reagent are used in synthesis. They also feature in catalytic reactions, especially alkene metathesis, and are of value in both industrial heterogeneous and in homogeneous catalysis for laboratory- and industrial-scale preparation of fine chemicals.
Metal carbene complexes are often classified into two types. The Fischer carbenes, named after Ernst Otto Fischer, feature strong π-acceptors at the metal and are electrophilic at the carbene carbon atom. Schrock carbenes, named after Richard R. Schrock, are characterized by more nucleophilic carbene carbon centers; these species typically feature higher oxidation state (valency) metals. N-Heterocyclic carbenes (NHCs) were popularized following Arduengo's isolation of a stable free carbene in 1991. Reflecting the growth of the area, carbene complexes are now known with a broad range of different reactivities and diverse substituents. Often it is not possible to classify a carbene complex solely with regards to its electrophilicity or nucleophilicity.
The common features of Fischer carbenes are:
Examples include (CO)5W=COMePh and (OC)5Cr=C(NR2)Ph.
Fischer carbene complexes are related to the singlet form of carbenes, where both electrons occupy the same sp2 orbital at the carbon. This lone pair donates to a metal-based empty d orbital, forming a σ bond. π-backbonding from a filled metal d orbital to the empty p orbital of the carbon atom is possible. However this interaction is generally weak since the alpha donor atoms also donate to this orbital. As such, Fischer carbenes are characterized as having partial double bond character. The major resonance structures of Fischer carbenes put the negative charge on the metal centre, and the positive on the carbon atom, making it electrophilic.
Fischer carbenes can be likened to ketones, with the carbene carbon atom being electrophilic, like the carbonyl carbon atom of a ketone. This can be seen from the resonance structures, where there is a significant contribution from the structure bearing a positive carbon centre. Like ketones, Fischer carbene species can undergo aldol-like reactions. The hydrogen atoms attached to the carbon atom α to the carbene carbon atom are acidic, and can be deprotonated by a base such as n-butyllithium, to give a nucleophile, which can undergo further reaction.
Schrock carbenes do not have π-accepting ligands on the metal centre. They are often called alkylidene complexes. Typically this subset of carbene complexes are found with:
Examples include ((CH3)3CCH2)Ta=CHC(CH3)3 and Os(PPh3)2(NO)Cl(=CH2).