Computational study on atom-economic alkyne hydrotelluration reaction using benchmarked ECP for Te

• Published in: Journal of molecular graphics & modelling Vol. 100; p. 107659
• Main Authors: Jayasree, Elambalassery G., Aswathy, Mohanan
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 01.11.2020
• Subjects: Calibration; ECP; Hydrotelluration; Regio- and stereoselectivity; Vinyl tellurides; Regio- and stereoselectivity; Hydrotelluration; ECP; Calibration; Vinyl tellurides
• ISSN: 1093-3263; 1873-4243
• DOI: 10.1016/j.jmgm.2020.107659

Geometry and energy calibration studies are done for arriving at a proper ECP for tellurium containing compounds. Among the various d-function included ECPs cc-pwCVTZ-PP and def2-TZVP give more reliable results. Non-catalytic and base/radical initiated hydrotelluration reactions are computationally studied using the calibrated def2-TZVP, with a special focus on the regio-and stereoselective formation of vinyl tellurides. The explored gas phase reaction mechanism indicates the addition of tellurol to unsaturated carbon-carbon triple bond via a concerted transition structure. Regioselectivity has been noticeably realized in presence of both base and radical mediated hydrotelluration leading to Markovnikov and anti-Markovnikov product respectively. [Display omitted] •Performance of various ECPs in geometry and energy calculation of tellurium containing compounds is analyzed. .•Calibrated def2-TZVP is used for analyzing the mechanistic aspects of alkyne hydrotelluration reaction. .•Base and radical mediated alkyne hydrotelluration regioselectively leads to MKV and AMKV product respectively.