Isoselenocyanates versus Isothiocyanates and Isocyanates

Alkyl and aryl isoselenocyanates are well known intermediates in the synthesis of various organoselenium compounds, but the knowledge of the physicochemical properties of simple unsaturated derivatives is still fragmentary. Vinyl-, 2-propenyl-, and cyclopropyl isoselenocyanates have been prepared by reaction of selenium in powder with the corresponding isocyanides. The isoselenocyanates of this series, with a variable distance between the N═C═Se group and the unsaturated or pseudounsaturated group, have been studied by UV-photoelectron spectroscopy and quantum-chemical calculations. For each of these three isoselenocyanates, the exploration of conformers and geometrical optimization always converge toward only one local minimum. The vinyl and cyclopropyl derivatives are characterized by similar order of magnitude of interactions between the NCSe group and the substituent, while for allylic compound two noninteracting moieties should be considered. The same conclusions were obtained for vinylic and cyclopropylic sulfur and oxygen derivatives. Thus the type and extent of interactions between the N═C═X (X = O, S, Se) group and an unsaturated (vinyl, allyl, or cyclopropyl) moiety are now clarified.