In chemistry, mesoionic carbenes (MICs) are a type of reactive intermediate that are related to N-heterocyclic carbenes (NHCs); thus, MICs are also referred to as abnormal N-heterocyclic carbenes (aNHCs) or remote N-heterocyclic carbenes (rNHCs). Unlike simple NHCs, the canonical resonance structures of these carbenes are mesoionic: an MIC cannot be drawn without adding additional charges to some of the atoms. A variety of free carbenes can be isolated and are stable at room temperature. Other free carbenes are not stable and are susceptible to intermolecular decomposition pathways. MICs do not dimerize according to Wanzlick equilibrium as do normal NHCs. This results in relaxed steric requirements for mesoionic carbenes as compared to NHCs. There are several mesoionic carbenes that cannot be generated as free compounds, but can be synthesized as a ligand in a transition metal complex. Most MIC transition metal complexes are less sensitive to air and moisture than phosphine or normal NHC complexes. They are also resistant to oxidation. The robust nature of MIC complexes is due to the ligand’s strong σ-donating ability. They are stronger σ-donors than phosphines, as well as normal N-heterocyclic carbenes due to decreased heteroatom stabilization. The strength of carbene ligands is attributed to the electropositive carbon center that forms strong bonds of a covalent nature with the metal. They have been shown to lower the frequency of CO stretching vibrations in metal complexes and exhibit large trans effects.
Classes
Imidazolin-4-ylidenes The most studied mesoionic carbenes are based on imidazole and are referred to as imidazolin-4-ylidenes. These complexes were first reported by Crabtree in 2001. The formation of imidazolin-4-ylidenes (MIC) instead of imidazolin-2-ylidenes (NHC) is typically a matter of blocking the C2 position. Most imidazolin-4-ylidenes are trisubstituted in the N1, C2, and N3 positions or tetrasubstituted. Electron-withdrawing groups in the N3 and C5 positions stabilize the carbenes more than electron-donating groups. Free carbenes as well as numerous transition metal complexes have been synthesized.
1,2,3-triazolylidenes Also well studied are the mesoionic carbenes based on 1,2,3-triazole, referred to as 1,2,3-triazol-4(or 5)-ylidenes. The first triazolylidenes were reported by Albrecht in 2008. These carbenes are typically trisubstituted with alkyl groups in the N1 and N3 positions and an aryl group in the C4 or C5 position. Free carbenes as well as numerous transition metal complexes have been reported. Free carbenes that are alkylated at N3 tend to undergo decomposition reactions in which the alkyl group participates in a nucleophilic attack at the carbene position. If N3 is substituted with a bulky alkyl group or an aryl group, the stability of the carbene increases significantly.
Pyrazolinylidenes The first mesoionic carbenes based on pyrazole have been reported by Huynh in 2007. These carbenes are referred to as pyrazolin-3(or 4)-ylidenes. Pyrazolin-4-ylidenes are often tetrasubstituted with alkyl or aryl groups; however, the C3 and C5 positions could be substituted with nitrogen- or oxygen-based groups. The electronic properties of the groups in the C3 and C5 positions affect the overall electron properties of the ligand and influence catalytic activity. Free carbene have been produced as well as transition metal complexes.
Others Examples of tetrazol-5-ylidenes based on tetrazole have been prepared by Araki. The N1 and N3 positions are substituted with alkyl or aryl groups. Transition metal complexes of these carbenes have been generated in situ. Mesoionic carbenes based on isoxazole and thiazole have been reported by Albrecht and Bertrand respectively. The isoxazol-4-ylidenes are trisubstituted in the N2, C3, and C5 positions with alkyl groups. The thiazol-5-ylidenes are trisubstituted in the C2, N3, and C4 positions with aryl groups. Transition metal complexes of both types of carbenes have been generated in situ. Bertrand also reported a 1,3-dithiol-5-ylidene based on 1,3-dithiolane, but it can only be isolated as a transition metal complex.
Synthesis of free carbenes
Many free mesoionic carbenes are synthesized from their protonated salt form by deprotonation using strong potassium bases, such as potassium bis(trimethylsilyl)amide (KHMDS) or potassium tert-butoxide (KOt-Bu). Potassium bases are used because they do not form stable carbene-alkali metal adducts. Imidazolin-4-ylidenes (MIC) would form rather than imidazolin-2-ylidenes (NHC) due to blocking the C2 position. The C2 carbenes are thermodynamically more stable than their C4 counterparts due to resonance and inductive carbon-nitrogen interactions. Also, calculations show that the C4 hydrogen is less acidic than the C2 hydrogen of imidazole. This data suggests that the C2 position should be activated preferentially to the C4 position unless the C2 position is blocked. Aryl and bulky alkyl groups (such as isopropyl) are good at blocking the C2 position from being activated.
Carbene metal complexes
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