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A theoretical investigation on the isomerism and the NMR properties of thiosemicarbazones

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Hybrid density functional theory calculations at the mPW1PW91/6-31+G(d,p) level of theory have been used to investigate the optimized structures and other molecular properties of five different series of thiosemicarbazones. The investigated compounds were obtained from acenaphthenequinone, isatin and its derivatives, and alloxan. The focus of the study is the isomerism and the NMR characterization of these thiosemicarbazones. It was found that only one isomer is expected for thiosemicarbazones and methylthiosemicarbazones, while for dimethylthiosemicarbazones, two isomers are possible. All investigated thiosemicarbazones exhibit a hydrazinic proton that is highly deshielded and resonates far downfield in the proton NMR spectra. This proton is a part of a characteristic sixmembered ring, and its NMR properties are a result of its strong, intermolecular hydrogen bond. The relationships between the calculated 1H and 13C NMR chemical shifts and various geometric parameters are reported. [...]

Opis fizyczny
  • Department of Chemistry, Tennessee Technological University, Cookeville, Tennessee, 38505, USA
  • Department of Chemistry, Tennessee Technological University, Cookeville, Tennessee, 38505, USA,
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  • [59] The Supplementary Material includes geometries in Cartesian coordinates, calculated isotropic magnetic shielding tensors, Mulliken and GAPT atomic charges, energetic parameters, and frequencies for all structures optimized in this work. This material can be obtained from the corresponding author by emailing your request to
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