2025/06/30 by Martin Hejda, Lukáš Doležal, Milan Erben +4 · 1 voice
Chemistry · Pharmacology, Toxicology and Pharmaceutics · #Crystallography and molecular interactions #Organoselenium and organotellurium chemistry #Synthesis and characterization of novel inorganic/organometallic compounds
paper · doi:10.1002/chem.202502141
openalex publication_date 2025/06/30 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/01
Abstract Redox catalysis involving the tellurenyl triflate [2‐( t BuNCH)C 6 H 4 Te][OTf] was utilized for the activation of the common silanes Et 3 SiH, Ph 4– n SiH n ( n = 1–3) as well as the difficult‐to‐handle gaseous SiH 4 . Furthermore, complex siloxanes containing multiple Si─H bonds were converted into siloxylated phenols, which are of high interest for the chemical industry. Insights into the catalytic cycle utilizing para ‐quinones as both oxidants and substrates were provided by identification of key intermediates and by using in situ time‐resolved FTIR spectroscopy, NMR spectroscopy, single‐crystal X‐ray diffraction analysis, and DFT calculations. Based on this study, the catalytic cycle is initiated by a Si─H bond activation resulting in the formation of a ditelluride species and the corresponding silyl triflate. In turn, the ditelluride species is first oxidized by the presented quinone, forming an unprecedented tellurium‐based oxonium intermediate, resulting in the formation of the siloxylated phenols and liberation of the tellurium catalyst upon subsequent reaction with the silyl triflate. Our proposed catalytic cycle can be generalized for any silane used in this study.