Computational investigation of cobalt and copper bis (oxothiolene) complexes as an alternative for olefin purification
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Considering that olefins present a large volume feedstock, it is reasonable to expect that their purification is industrially critical. After the discovery of the nickel bis (dithiolene) complex Ni(S2C2(CF3)2)2 that exhibits electro-catalytic activity with olefins but tends to decompose by a competitive reaction route, related complexes have been explored experimentally and theoretically. In this paper, a computational examination is performed on differently charged cobalt and copper bis (oxothiolene) complexes [M (OSC2(CN)2)2] to test their potential applicability as the catalysts for olefin purification, using the simplest olefin, ethylene. Possible reaction pathways for ethylene addition on these complexes were explored, to determine whether some of these candidates can avoid the reaction route that leads to decomposition, which is distinctive from the nickel complex, and to form stable adducts that can subsequently release ethylene by reduction. Our calculations suggest that the ne...utral cobalt complex might be an alternative catalyst, because all its forms can bind ethylene to produce stable interligand adducts with moderate to low activation barriers, rather than to form intraligand adducts that lead to decomposition. The calculations also predict that these interligand adducts are capable of releasing ethylene upon reduction. In addition, it can produce the desired interligand adducts following two different reaction pathways, assigned as the direct and the indirect, with no need for anion species as co-catalysts, which is crucial for the nickel complex. Thus, the olefin purification process could be much simpler by using this catalyst.
Ključne reči:
Olefin purification / Density functional theory / Reaction mechanisms / Electro-catalystIzvor:
Journal of Molecular Modeling, 2020, 26, 8, 205-Finansiranje / projekti:
- Qatar National Library
- Qatar National Research Fund through the NPRP [8-028-1-001]
- Qatar National Research Fund through the NPRP [5-318-1-063]
DOI: 10.1007/s00894-020-04445-x
ISSN: 1610-2940
PubMed: 32651713
WoS: 000546931100001
Scopus: 2-s2.0-85087884881
Institucija/grupa
VinčaTY - JOUR AU - Sredojević, Dušan AU - Raju, Rajesh K AU - Moncho, Salvador AU - Belić, Milivoj R. AU - Brothers, Edward N. PY - 2020 UR - https://vinar.vin.bg.ac.rs/handle/123456789/9084 AB - Considering that olefins present a large volume feedstock, it is reasonable to expect that their purification is industrially critical. After the discovery of the nickel bis (dithiolene) complex Ni(S2C2(CF3)2)2 that exhibits electro-catalytic activity with olefins but tends to decompose by a competitive reaction route, related complexes have been explored experimentally and theoretically. In this paper, a computational examination is performed on differently charged cobalt and copper bis (oxothiolene) complexes [M (OSC2(CN)2)2] to test their potential applicability as the catalysts for olefin purification, using the simplest olefin, ethylene. Possible reaction pathways for ethylene addition on these complexes were explored, to determine whether some of these candidates can avoid the reaction route that leads to decomposition, which is distinctive from the nickel complex, and to form stable adducts that can subsequently release ethylene by reduction. Our calculations suggest that the neutral cobalt complex might be an alternative catalyst, because all its forms can bind ethylene to produce stable interligand adducts with moderate to low activation barriers, rather than to form intraligand adducts that lead to decomposition. The calculations also predict that these interligand adducts are capable of releasing ethylene upon reduction. In addition, it can produce the desired interligand adducts following two different reaction pathways, assigned as the direct and the indirect, with no need for anion species as co-catalysts, which is crucial for the nickel complex. Thus, the olefin purification process could be much simpler by using this catalyst. T2 - Journal of Molecular Modeling T1 - Computational investigation of cobalt and copper bis (oxothiolene) complexes as an alternative for olefin purification VL - 26 IS - 8 SP - 205 DO - 10.1007/s00894-020-04445-x ER -
@article{ author = "Sredojević, Dušan and Raju, Rajesh K and Moncho, Salvador and Belić, Milivoj R. and Brothers, Edward N.", year = "2020", abstract = "Considering that olefins present a large volume feedstock, it is reasonable to expect that their purification is industrially critical. After the discovery of the nickel bis (dithiolene) complex Ni(S2C2(CF3)2)2 that exhibits electro-catalytic activity with olefins but tends to decompose by a competitive reaction route, related complexes have been explored experimentally and theoretically. In this paper, a computational examination is performed on differently charged cobalt and copper bis (oxothiolene) complexes [M (OSC2(CN)2)2] to test their potential applicability as the catalysts for olefin purification, using the simplest olefin, ethylene. Possible reaction pathways for ethylene addition on these complexes were explored, to determine whether some of these candidates can avoid the reaction route that leads to decomposition, which is distinctive from the nickel complex, and to form stable adducts that can subsequently release ethylene by reduction. Our calculations suggest that the neutral cobalt complex might be an alternative catalyst, because all its forms can bind ethylene to produce stable interligand adducts with moderate to low activation barriers, rather than to form intraligand adducts that lead to decomposition. The calculations also predict that these interligand adducts are capable of releasing ethylene upon reduction. In addition, it can produce the desired interligand adducts following two different reaction pathways, assigned as the direct and the indirect, with no need for anion species as co-catalysts, which is crucial for the nickel complex. Thus, the olefin purification process could be much simpler by using this catalyst.", journal = "Journal of Molecular Modeling", title = "Computational investigation of cobalt and copper bis (oxothiolene) complexes as an alternative for olefin purification", volume = "26", number = "8", pages = "205", doi = "10.1007/s00894-020-04445-x" }
Sredojević, D., Raju, R. K., Moncho, S., Belić, M. R.,& Brothers, E. N.. (2020). Computational investigation of cobalt and copper bis (oxothiolene) complexes as an alternative for olefin purification. in Journal of Molecular Modeling, 26(8), 205. https://doi.org/10.1007/s00894-020-04445-x
Sredojević D, Raju RK, Moncho S, Belić MR, Brothers EN. Computational investigation of cobalt and copper bis (oxothiolene) complexes as an alternative for olefin purification. in Journal of Molecular Modeling. 2020;26(8):205. doi:10.1007/s00894-020-04445-x .
Sredojević, Dušan, Raju, Rajesh K, Moncho, Salvador, Belić, Milivoj R., Brothers, Edward N., "Computational investigation of cobalt and copper bis (oxothiolene) complexes as an alternative for olefin purification" in Journal of Molecular Modeling, 26, no. 8 (2020):205, https://doi.org/10.1007/s00894-020-04445-x . .