The addition reactions between N-heterocyclic carbenes and fullerenes (C60 and C70): a density functional study

Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts.

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In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C₆₀ Fullerenes

Martínez

Vummaleti

Falivene

et al. 2016

Chemistry A European J

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Exohedral functionalization of endohedral metallofullerenes: Interplay between inside and outside

Jin

Liu

Magagula

et al. 2019

Coordination Chemistry Reviews

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A comparative study on the N-heterocyclic carbene adducts of I_h-C₆₀, D_5h-C₇₀ and Sc₃N@I_h-C₈₀

Jin

Yang

Liu

et al. 2017

Phys. Chem. Chem. Phys.

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We found that the standard B3LYP and dispersion-corrected B3LYP-D3 methods predicted completely opposite energy order for the Lewis acid-base adducts formed by I-C or D-C with normal C2-bound (nNHC) and abnormal C5-bound (aNHC) N-heterocyclic carbenes. By using the validated B3LYP-D3 method and taking the solvent effects into account, the exclusive formations of the nNHC-C (Li et al. J. Am. Chem. Soc., 2011, 133, 12410-12413) and aNHC-ScN@I-C complexes (Chen et al. Chem. Sci., 2016, 7, 2331-2334) in two recent experiments were suggested to be thermodynamically and kinetically controlled, respectively. In contrast to the reported reactions of endohedral metallofullerenes, aNHC-ScN@I-C hardly isomerizes to the low-energy normal adducts under heat treatment probably due to the substantial energy barrier and excess NHC reagent used in the experiment. Furthermore, the highly regioselective addition of aNHC to the triple-hexagon-junction carbon atom of ScN@I-C was rationalized by using the frontier molecular orbital theory.

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The addition reactions between N-heterocyclic carbenes and fullerenes (C60 and C70): a density functional study

Cited by 3 publications

References 15 publications

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C₆₀ Fullerenes

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C₆₀ Fullerenes

Exohedral functionalization of endohedral metallofullerenes: Interplay between inside and outside

A comparative study on the N-heterocyclic carbene adducts of I_h-C₆₀, D_5h-C₇₀ and Sc₃N@I_h-C₈₀

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The addition reactions between N-heterocyclic carbenes and fullerenes (C60 and C70): a density functional study

Cited by 3 publications

References 15 publications

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C60 Fullerenes

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C60 Fullerenes

Exohedral functionalization of endohedral metallofullerenes: Interplay between inside and outside

A comparative study on the N-heterocyclic carbene adducts of Ih-C60, D5h-C70 and Sc3N@Ih-C80

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In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C₆₀ Fullerenes

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C₆₀ Fullerenes

A comparative study on the N-heterocyclic carbene adducts of I_h-C₆₀, D_5h-C₇₀ and Sc₃N@I_h-C₈₀