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Electrospray ionization mass spectrometric characterization of key Te(IV) cationic intermediates for the addition of TeCl 4 to alkynes
Author(s) -
Santos Leonardo S.,
Cunha Rodrigo L. O. R.,
Comasseto João V.,
Eberlin Marcos N.
Publication year - 2007
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.2984
Subject(s) - chemistry , electrophile , cationic polymerization , electrospray ionization , tetrahydrofuran , mass spectrometry , medicinal chemistry , organic chemistry , chromatography , catalysis , solvent
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 TeCl 4 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 TeCl 3 +in tetrahydrofuran (THF) solutions of TeCl 4 , 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.