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Steric maps to evaluate the role of steric hindrance on the IPr NHC ligand

(2013) Procedia Computer Science. 18. p.845-854
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Abstract
Density functional theory (DFT) calculations were used to predict and rationalize the effect of the modification of the structure of the prototype 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) (IPr) N-heterocyclic carbene (NHC) ligand. The modification consists in the substitution of the methyl groups of ortho isopropyl substituent with phenyl groups, and here we plan to describe how such significant changes effect the metal environment and therefore the related catalytic behaviour by simple steric maps. Bearing in mind that there is a significant structural difference between IPr and IPr* ligands, that translated in different reactivity for several olefin metathesis reactions, here by means of DFT we characterize where the NHC ligand plays a more active role and where it is a simple spectator, or at least its modification does not significantly change its catalytic role/performance. Furthermore, this communication endeavours to modify further the skeleton of the IPr NHC ligand. The optimization of these bulky new systems go to the limits of the DFT computational method.
Keywords
N-HETEROCYCLIC CARBENE, IPr, CATALYZED OLEFIN METATHESIS, RUTHENIUM-INDENYLIDENE COMPLEXES, RU(II) COMPLEXES, O-2 ACTIVATION, MECHANISM, REACTIVITY, BEARING, ENERGY, METAL, NHC ligand, DFT calculations, olefins metathesis, ruthenium catalysts

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Chicago
Poater, Albert, Laura Falivene, César Alejandro Urbina Blanco, Simone Manzini, Steven Nolan, and Luigi Cavallo. 2013. “Steric Maps to Evaluate the Role of Steric Hindrance on the IPr NHC Ligand.” In Procedia Computer Science, 18:845–854. Amsterdam, Netherlands: Elsevier Science BV.
APA
Poater, A., Falivene, L., Urbina Blanco, C. A., Manzini, S., Nolan, S., & Cavallo, L. (2013). Steric maps to evaluate the role of steric hindrance on the IPr NHC ligand. Procedia Computer Science (Vol. 18, pp. 845–854). Presented at the 13th Annual International Conference on Computational Science (ICCS), Amsterdam, Netherlands: Elsevier Science BV.
Vancouver
1.
Poater A, Falivene L, Urbina Blanco CA, Manzini S, Nolan S, Cavallo L. Steric maps to evaluate the role of steric hindrance on the IPr NHC ligand. Procedia Computer Science. Amsterdam, Netherlands: Elsevier Science BV; 2013. p. 845–54.
MLA
Poater, Albert, Laura Falivene, César Alejandro Urbina Blanco, et al. “Steric Maps to Evaluate the Role of Steric Hindrance on the IPr NHC Ligand.” Procedia Computer Science. Vol. 18. Amsterdam, Netherlands: Elsevier Science BV, 2013. 845–854. Print.
@inproceedings{8201941,
  abstract     = {Density functional theory (DFT) calculations were used to predict and rationalize the effect of the modification of the structure of the prototype 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) (IPr) N-heterocyclic carbene (NHC) ligand. The modification consists in the substitution of the methyl groups of ortho isopropyl substituent with phenyl groups, and here we plan to describe how such significant changes effect the metal environment and therefore the related catalytic behaviour by simple steric maps. Bearing in mind that there is a significant structural difference between IPr and IPr* ligands, that translated in different reactivity for several olefin metathesis reactions, here by means of DFT we characterize where the NHC ligand plays a more active role and where it is a simple spectator, or at least its modification does not significantly change its catalytic role/performance. Furthermore, this communication endeavours to modify further the skeleton of the IPr NHC ligand. The optimization of these bulky new systems go to the limits of the DFT computational method.},
  author       = {Poater, Albert and Falivene, Laura and Urbina Blanco, C{\'e}sar Alejandro and Manzini, Simone and Nolan, Steven and Cavallo, Luigi},
  booktitle    = {Procedia Computer Science},
  issn         = {1877-0509},
  keyword      = {N-HETEROCYCLIC CARBENE,IPr,CATALYZED OLEFIN METATHESIS,RUTHENIUM-INDENYLIDENE COMPLEXES,RU(II) COMPLEXES,O-2 ACTIVATION,MECHANISM,REACTIVITY,BEARING,ENERGY,METAL,NHC ligand,DFT calculations,olefins metathesis,ruthenium catalysts},
  language     = {eng},
  location     = {Barcelona, SPAIN},
  pages        = {845--854},
  publisher    = {Elsevier Science BV},
  title        = {Steric maps to evaluate the role of steric hindrance on the IPr NHC ligand},
  url          = {http://dx.doi.org/10.1016/j.procs.2013.05.249},
  volume       = {18},
  year         = {2013},
}

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