Functionalized tellurols: synthesis, spectroscopic characterization by photoelectron spectroscopy, and quantum chemical study.
Ethene-, cyclopropane-, 3-butene-, and cyclopropanemethanetellurol have been synthesized by reaction of tributyltin hydride with the corresponding ditellurides and characterized by 1H, 13C, and 125Te NMR spectroscopy and high-resolution mass spectrometry. The tellurols of this series, with a gradually increasing distance between the tellurium atom and the unsaturated group, have been studied by photoelectron spectroscopy and quantum chemical calculations. Two stable conformations of ethenetellurol and cyclopropanetellurol, five of allyltellurol, and four of cyclopropanemethanetellurol were found. In the photoelectron spectrum of vinyltellurol, the huge split between the first two bands indicates a direct interaction between the tellurium lone electron pair and the double bond. In the allyl derivative, a hyperconjugation effect was found for the most stable conformers. In contrast to the vinyl compounds, no direct interaction between the lone electron pair of X (X = O, S, Se, and Te) and the three-membered ring could be observed in the cyclopropyl derivatives. A hyperconjugation-like effect, which is independent of the relative orientation of the X-H group, is found to increase from S to Te. Thus, the type and extent of the interaction between the TeH group and an unsaturated or cyclopropyl moiety are clarified while the first comparison of interactions between the nonradioactive unsaturated chalcogen derivatives is performed.
Khater
Brahim
B
Sciences Chimiques de Rennes, Ecole Nationale Supérieure de Chimie de Rennes, Centre National de la Recherche Scientifique (CNRS), 35700 Rennes, France.
Guillemin
Jean-Claude
JC
Bajor
Gábor
G
Veszprémi
Tamás
T