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In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C 60 Fullerenes
Author(s) -
Martínez Juan Pablo,
Vummaleti Sai Vikrama Chaitanya,
Falivene Laura,
Nolan Steven P.,
Cavallo Luigi,
Solà Miquel,
Poater Albert
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600383
Subject(s) - carbene , steric effects , chemistry , catalysis , ligand (biochemistry) , metathesis , olefin fiber , olefin metathesis , combinatorial chemistry , electronic effect , stereochemistry , medicinal chemistry , organic chemistry , polymerization , receptor , biochemistry , polymer
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 C 60 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.