What Happens Without Nickel? Cyclization Reactions of Ethylene with Ethanedithial and Related Molecules

被引：0

作者：

Shibl, Mohamed F. ^{[1
,3
]}

Moncho, Salvador ^{[2
]}

Brothers, Edward N. ^{[2
]}

机构：

[1] Qatar Univ, Coll Engn, Dept Chem, Doha, Qatar

[2] Texas A&M Univ Qatar, Dept Chem, Doha, Qatar

[3] Cairo Univ, Fac Sci, Dept Chem, Cairo, Egypt

来源：

JOURNAL OF COMPUTATIONAL CHEMISTRY | 2018年 / 39卷 / 18期

关键词：

olefin; benchmarking; cyclization; isomerization; density functional; GENERALIZED GRADIENT APPROXIMATION; BASIS-SET CONVERGENCE; HYBRID DENSITY FUNCTIONALS; BIS(DITHIOLENE) COMPLEX; CORRELATED CALCULATIONS; HARTREE-FOCK; MECHANISM; ENERGY; THERMOCHEMISTRY;

D O I：

10.1002/jcc.25142

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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 B97XD, and the effect of the basis set is also investigated for it. (c) 2017 Wiley Periodicals, Inc.

引用

页码：1158 / 1167

页数：10