Alkenyl selenols and selenocyanates: synthesis, spectroscopic characterization by photoelectron spectroscopy, and quantum chemical study |
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Authors: | Bajor Gábor Veszprémi Tamás Riague El Hassan Guillemin Jean-Claude |
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Institution: | Budapest University of Technology and Economics, 1521 Budapest, Gellért tér 4, Hungary. |
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Abstract: | Vinyl, allyl, and homoallyl selenols were easily prepared by a chemoselective reduction of the corresponding selenocyanates with aluminum hydrides. Two stable vinyl and five stable allyl conformers of both series were predicted on the potential-energy surface. The interaction of SeH or SeCN groups with the vinyl group has been investigated with UV photoelectron spectroscopy and quantum chemical calculations, using the MP2/cc-pVTZ and B3LYP/cc-pVTZ levels. In the vinyl derivatives, a surprisingly strong direct conjugation of the selenium lone electron pair and the C=C double bond was observed. On the other hand, in allyl position the selenium lone pair is independent on the C=C double bond, and the hyperconjugation between the Se-C bond and the double bond is the ruling effect. Thus is clarified the type and extent of the interaction between the SeH or SeCN group and the unsaturated moiety. |
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Keywords: | ab initio calculations photoelectron spectroscopy selenium selenocyanates selenols |
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