What Happens Without Nickel? Cyclization Reactions of Ethylene with Ethanedithial and Related Molecules. Issue 18 (22nd December 2017)

• Record Type: Journal Article
• Authors: Shibl, Mohamed F.; Moncho, Salvador; Brothers, Edward N.
• Other Names: Matta Chérif F. guestEditor.; Massa Lou guestEditor.
• Is Part Of: Journal of computational chemistry. Volume 39:Issue 18(2018)
• Page Start: 1158
• Page End: 1167
• Publication Date: 2017-12-22
• Subjects: olefin -- benchmarking -- cyclization -- isomerization -- density functional; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.25142
• Languages: English
• ISSNs: 0192-8651

Abstract

Abstract : We present a computational study of the mechanism of the formation of 6‐member heterocycles through the binding of ethylene to oxaldehyde, ethanedithial, and 2‐thioxoacetaldehyde. This process is related to the olefin separation technology by metal dithiolenes and dioxolenes, being the formation of those heterocycles the main decomposition route. We also present a benchmark of 26 density functionals (spanning hybrid, double‐hybrid, range‐separated, semilocal, and local functionals) related to CCSD(T)/CBS reference values. Both the cyclization reaction and the isomerization of the cyclic product are included in the benchmark. The best functional among those tested for these reactions is ω B97XD, and the effect of the basis set is also investigated for it. © 2017 Wiley Periodicals, Inc. Abstract : Olefins can be reversibly bound by metal dithiolenes and related compounds such as oxaldehyde, ethanedithial, and 2‐thioxoacetaldehyde to form cyclic systems. A benchmarking study of various functionals for modeling this process is done. The lack of metal atoms in this study makes the target CCSD(T) values more reliable due to a lack of multi‐reference character. The best functional among those tested for these reactions is wB97XD. The cyclization reaction has found to be more favorable in the system with two sulfur atoms, both kinetically and thermodynamically. Isomerization of the heterocycle between two equivalent symmetric conformations of the DHD product is also found to be more favorable for SS system, but difference is low.