Alkenyl selenols and selenocyanates: synthesis, spectroscopic characterization by photoelectron spectroscopy, and quantum chemical study.
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.
Bajor
Gábor
G
Budapest University of Technology and Economics, 1521 Budapest, Gellért tér 4, Hungary.
Veszprémi
Tamás
T
Riague
El Hassan
el H
Guillemin
Jean-Claude
JC