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Alkenyl Selenols and Selenocyanates: Synthesis, Spectroscopic Characterization by Photoelectron Spectroscopy, and Quantum Chemical Study
Author(s) -
Bajor Gábor,
Veszprémi Tamás,
Riague El Hassan,
Guillemin JeanClaude
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400159
Subject(s) - x ray photoelectron spectroscopy , quantum chemical , characterization (materials science) , chemistry , spectroscopy , organic chemistry , nanotechnology , materials science , chemical engineering , physics , molecule , engineering , quantum mechanics
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 CC double bond was observed. On the other hand, in allyl position the selenium lone pair is independent on the CC double bond, and the hyperconjugation between the SeC 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.