Computational investigation of cobalt and copper bis (oxothiolene) complexes as an alternative for olefin purification

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(S(2)C(2)(CF(3))(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 (OSC(2)(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. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (10.1007/s00894-020-04445-x) contains supplementary material, which is available to authorized users.