title: Computational exploration of alternative catalysts for olefin purification: cobalt and copper analogues inspired by nickel bis(dithiolene) electrocatalysis.
abstract: Olefin purification is an important process in petrochemistry. The behavior of the nickel bis(dithiolene) complex Ni(S2C2(CF3)2)2 (1(_Ni)) as an electrocatalyst for this process was thoroughly explored experimentally and computationally. Here, computational investigations with the ωB97X-D functional were conducted to explore alternative candidates [M(S2C2(CF3)2)2](n) (M = Co with n = 0, -1, -2, -3 and Cu with n = +1, 0, -1, -2) for olefin purification by using ethylene as a model. The reaction mechanism for these alternative catalysts was calculated to determine if any of these alternatives could block the decomposition route that exists for the Ni catalyst, bind ethylene efficiently to form the adducts, and release ethylene upon reduction. Calculations predict that the neutral cobalt complex 1(_Co) binds and releases olefin upon reduction with low activation barriers. Furthermore, 1(_Co), unlike 1(_Ni), catalyzes the desired reaction without the need of the anion as a cocatalyst. The Co atom directly coordinates with ethylene more favorably than Ni, facilitating the indirect pathway that is found to lead to the formation of the desired interligand adduct. The reduction and oxidation processes involved in the reaction are computed to occur under reasonable experiment conditions. Among the copper complexes, the calculations predict that the anionic copper complex 1(_Cu)(-) also may be an alternative catalyst, whose performance is somewhat worse than 1(_Ni). The reaction of 1(_Cu)(-) with ethylene is predicted to be thermodynamically neutral. New catalysts that need no electrochemical regenerations may be possible by designing appropriate dithiolene ligands for 1(_Cu)(-).
authors.affiliation: Department of Chemistry, Texas A&M University , College Station, Texas 77843, United States.
authors.forename: Haixia
authors.initials: H
authors.lastname: Li
authors.forename: Edward N
authors.initials: EN
authors.lastname: Brothers
authors.forename: Michael B
authors.initials: MB
authors.lastname: Hall