Why Low Valent Lead(II) Hydride Complex Would be a Better Catalyst for CO2 Activation than Its 14 Group Analogues?

Nery Villegas-Escobar, Daniela E. Ortega, Diego Cortés-Arriagada, Rocío Durán, Diana Yepes, Soledad Gutiérrez-Oliva, Alejandro Toro-Labbé

Resultado de la investigación: Article

Resumen

A low valent Pb(II) hydride complex with NacNac ligand (NacNac = [ArNC(Me)CHC (Me)NAr]-, with Ar = 2,6-iPr2C6H3) is predicted to be the best catalyst for CO2 activation compared to its Ge(II) and Sn(II) analogues, which have been experimentally reported (Jana, A., et al. J. Am. Chem. Soc. 2009, 131, 1288;Jana, A. et al. Angew. Chem. Int. Ed. 2009, 48, 1106). The CO2 activation mechanism mediated by Ge(II), Sn(II) and Pb(II) catalysts was studied in toluene using density functional theory calculations. The results show that the activation can be carried out through two reaction pathways, giving rise to two different conformers which have been computationally predicted for the first time. In all the cases, the activation process was thermodynamically favored, in addition, the Pb(II) catalyst exhibited the lowest activation energy, compared with Ge(II), Sn(II), and even Si(II). Thus, it was found that, going down in group 14, the reactivity of the NacNac based complexes toward CO2 activation increases considerably. This result is due to the increase of the acidic character of the metal as the metal size increases causing a more polar δ+M-Hδ- bond, which allows an easier channel for the hydride transfer reaction. Interestingly, a linear dependence between activation energies and the polarity of the M-H bond was found. Additionally, a detailed characterization of possible interconversions between the products of activation helps to explain the X-ray structures obtained to date. Most importantly, it was found that the direct interconversion of the products obtained after the addition of CO2 from each reaction pathway is not possible, and can be reached by means of subsequent C-O and M-O bond torsions. Our calculations suggest that the CO2 activation catalyzed by Pb(II)-NacNac hydride complex would be both thermodynamically and kinetically viable. The reactivity trend found in this work contributes to the growing development of CO2 activation by transition metal-free catalysts.

Idioma originalEnglish
Páginas (desde-hasta)12127-12135
Número de páginas9
PublicaciónJournal of Physical Chemistry C
Volumen121
N.º22
DOI
EstadoPublished - 8 jun 2017

Huella dactilar

Hydrides
hydrides
Lead
Chemical activation
activation
analogs
catalysts
Catalysts
reactivity
Activation energy
Metals
activation energy
Toluene
products
Torsional stress
metals
torsion
Transition metals
Density functional theory
toluene

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Surfaces, Coatings and Films
  • Physical and Theoretical Chemistry

Citar esto

Villegas-Escobar, N., Ortega, D. E., Cortés-Arriagada, D., Durán, R., Yepes, D., Gutiérrez-Oliva, S., & Toro-Labbé, A. (2017). Why Low Valent Lead(II) Hydride Complex Would be a Better Catalyst for CO2 Activation than Its 14 Group Analogues? Journal of Physical Chemistry C, 121(22), 12127-12135. https://doi.org/10.1021/acs.jpcc.7b00278
Villegas-Escobar, Nery ; Ortega, Daniela E. ; Cortés-Arriagada, Diego ; Durán, Rocío ; Yepes, Diana ; Gutiérrez-Oliva, Soledad ; Toro-Labbé, Alejandro. / Why Low Valent Lead(II) Hydride Complex Would be a Better Catalyst for CO2 Activation than Its 14 Group Analogues?. En: Journal of Physical Chemistry C. 2017 ; Vol. 121, N.º 22. pp. 12127-12135.
@article{d06d2e083906476288ed2ee3517f0cca,
title = "Why Low Valent Lead(II) Hydride Complex Would be a Better Catalyst for CO2 Activation than Its 14 Group Analogues?",
abstract = "A low valent Pb(II) hydride complex with NacNac ligand (NacNac = [ArNC(Me)CHC (Me)NAr]-, with Ar = 2,6-iPr2C6H3) is predicted to be the best catalyst for CO2 activation compared to its Ge(II) and Sn(II) analogues, which have been experimentally reported (Jana, A., et al. J. Am. Chem. Soc. 2009, 131, 1288;Jana, A. et al. Angew. Chem. Int. Ed. 2009, 48, 1106). The CO2 activation mechanism mediated by Ge(II), Sn(II) and Pb(II) catalysts was studied in toluene using density functional theory calculations. The results show that the activation can be carried out through two reaction pathways, giving rise to two different conformers which have been computationally predicted for the first time. In all the cases, the activation process was thermodynamically favored, in addition, the Pb(II) catalyst exhibited the lowest activation energy, compared with Ge(II), Sn(II), and even Si(II). Thus, it was found that, going down in group 14, the reactivity of the NacNac based complexes toward CO2 activation increases considerably. This result is due to the increase of the acidic character of the metal as the metal size increases causing a more polar δ+M-Hδ- bond, which allows an easier channel for the hydride transfer reaction. Interestingly, a linear dependence between activation energies and the polarity of the M-H bond was found. Additionally, a detailed characterization of possible interconversions between the products of activation helps to explain the X-ray structures obtained to date. Most importantly, it was found that the direct interconversion of the products obtained after the addition of CO2 from each reaction pathway is not possible, and can be reached by means of subsequent C-O and M-O bond torsions. Our calculations suggest that the CO2 activation catalyzed by Pb(II)-NacNac hydride complex would be both thermodynamically and kinetically viable. The reactivity trend found in this work contributes to the growing development of CO2 activation by transition metal-free catalysts.",
author = "Nery Villegas-Escobar and Ortega, {Daniela E.} and Diego Cort{\'e}s-Arriagada and Roc{\'i}o Dur{\'a}n and Diana Yepes and Soledad Guti{\'e}rrez-Oliva and Alejandro Toro-Labb{\'e}",
year = "2017",
month = "6",
day = "8",
doi = "10.1021/acs.jpcc.7b00278",
language = "English",
volume = "121",
pages = "12127--12135",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "22",

}

Villegas-Escobar, N, Ortega, DE, Cortés-Arriagada, D, Durán, R, Yepes, D, Gutiérrez-Oliva, S & Toro-Labbé, A 2017, 'Why Low Valent Lead(II) Hydride Complex Would be a Better Catalyst for CO2 Activation than Its 14 Group Analogues?', Journal of Physical Chemistry C, vol. 121, n.º 22, pp. 12127-12135. https://doi.org/10.1021/acs.jpcc.7b00278

Why Low Valent Lead(II) Hydride Complex Would be a Better Catalyst for CO2 Activation than Its 14 Group Analogues? / Villegas-Escobar, Nery; Ortega, Daniela E.; Cortés-Arriagada, Diego; Durán, Rocío; Yepes, Diana; Gutiérrez-Oliva, Soledad; Toro-Labbé, Alejandro.

En: Journal of Physical Chemistry C, Vol. 121, N.º 22, 08.06.2017, p. 12127-12135.

Resultado de la investigación: Article

TY - JOUR

T1 - Why Low Valent Lead(II) Hydride Complex Would be a Better Catalyst for CO2 Activation than Its 14 Group Analogues?

AU - Villegas-Escobar, Nery

AU - Ortega, Daniela E.

AU - Cortés-Arriagada, Diego

AU - Durán, Rocío

AU - Yepes, Diana

AU - Gutiérrez-Oliva, Soledad

AU - Toro-Labbé, Alejandro

PY - 2017/6/8

Y1 - 2017/6/8

N2 - A low valent Pb(II) hydride complex with NacNac ligand (NacNac = [ArNC(Me)CHC (Me)NAr]-, with Ar = 2,6-iPr2C6H3) is predicted to be the best catalyst for CO2 activation compared to its Ge(II) and Sn(II) analogues, which have been experimentally reported (Jana, A., et al. J. Am. Chem. Soc. 2009, 131, 1288;Jana, A. et al. Angew. Chem. Int. Ed. 2009, 48, 1106). The CO2 activation mechanism mediated by Ge(II), Sn(II) and Pb(II) catalysts was studied in toluene using density functional theory calculations. The results show that the activation can be carried out through two reaction pathways, giving rise to two different conformers which have been computationally predicted for the first time. In all the cases, the activation process was thermodynamically favored, in addition, the Pb(II) catalyst exhibited the lowest activation energy, compared with Ge(II), Sn(II), and even Si(II). Thus, it was found that, going down in group 14, the reactivity of the NacNac based complexes toward CO2 activation increases considerably. This result is due to the increase of the acidic character of the metal as the metal size increases causing a more polar δ+M-Hδ- bond, which allows an easier channel for the hydride transfer reaction. Interestingly, a linear dependence between activation energies and the polarity of the M-H bond was found. Additionally, a detailed characterization of possible interconversions between the products of activation helps to explain the X-ray structures obtained to date. Most importantly, it was found that the direct interconversion of the products obtained after the addition of CO2 from each reaction pathway is not possible, and can be reached by means of subsequent C-O and M-O bond torsions. Our calculations suggest that the CO2 activation catalyzed by Pb(II)-NacNac hydride complex would be both thermodynamically and kinetically viable. The reactivity trend found in this work contributes to the growing development of CO2 activation by transition metal-free catalysts.

AB - A low valent Pb(II) hydride complex with NacNac ligand (NacNac = [ArNC(Me)CHC (Me)NAr]-, with Ar = 2,6-iPr2C6H3) is predicted to be the best catalyst for CO2 activation compared to its Ge(II) and Sn(II) analogues, which have been experimentally reported (Jana, A., et al. J. Am. Chem. Soc. 2009, 131, 1288;Jana, A. et al. Angew. Chem. Int. Ed. 2009, 48, 1106). The CO2 activation mechanism mediated by Ge(II), Sn(II) and Pb(II) catalysts was studied in toluene using density functional theory calculations. The results show that the activation can be carried out through two reaction pathways, giving rise to two different conformers which have been computationally predicted for the first time. In all the cases, the activation process was thermodynamically favored, in addition, the Pb(II) catalyst exhibited the lowest activation energy, compared with Ge(II), Sn(II), and even Si(II). Thus, it was found that, going down in group 14, the reactivity of the NacNac based complexes toward CO2 activation increases considerably. This result is due to the increase of the acidic character of the metal as the metal size increases causing a more polar δ+M-Hδ- bond, which allows an easier channel for the hydride transfer reaction. Interestingly, a linear dependence between activation energies and the polarity of the M-H bond was found. Additionally, a detailed characterization of possible interconversions between the products of activation helps to explain the X-ray structures obtained to date. Most importantly, it was found that the direct interconversion of the products obtained after the addition of CO2 from each reaction pathway is not possible, and can be reached by means of subsequent C-O and M-O bond torsions. Our calculations suggest that the CO2 activation catalyzed by Pb(II)-NacNac hydride complex would be both thermodynamically and kinetically viable. The reactivity trend found in this work contributes to the growing development of CO2 activation by transition metal-free catalysts.

UR - http://www.scopus.com/inward/record.url?scp=85021434585&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcc.7b00278

DO - 10.1021/acs.jpcc.7b00278

M3 - Article

AN - SCOPUS:85021434585

VL - 121

SP - 12127

EP - 12135

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 22

ER -

Villegas-Escobar N, Ortega DE, Cortés-Arriagada D, Durán R, Yepes D, Gutiérrez-Oliva S y otros. Why Low Valent Lead(II) Hydride Complex Would be a Better Catalyst for CO2 Activation than Its 14 Group Analogues? Journal of Physical Chemistry C. 2017 jun 8;121(22):12127-12135. https://doi.org/10.1021/acs.jpcc.7b00278