Abstract

Tellurium tetrachloride adds to alkynes via two pathways: a concerted syn-addition that yields Z-tri-and -tetrasubstituted alkenes or an anti-addition that yields E-alkenes. The mechanistic aspects of these divergent pathways for TeCl4 addition to alkynes have been investigated by on-line electrospray ionization (tandem) mass spectrometry (ESI-MS(/MS)). Via ESI-MS(/MS), we have been able to intercept and characterize the active electrophile TeCl3 + in tetrahydrofuran (THF) solutions of TeCl4, as well as its THF complex and several TeCl x(OH)y + derivatives. For the first time, also, key Te(IV) cationic intermediates of the electrophilic addition of TeCl 4 to alkynes were captured for gas-phase MS investigation. The detailed structural data of cyclic tellurane intermediates intercepted herein seems to provide insights into the coordinative behavior of the Te(IV) atom and its mode of action towards biological targets. Copyright © 2007 John Wiley & Sons, Ltd.