Redox Cycling at Tellurium: Selective and Multiple Activation of Si―H Bonds in Common Organosilanes and SiH4

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F25%3A39923266" target="_blank" >RIV/00216275:25310/25:39923266 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1002/chem.202502141" target="_blank" >https://doi.org/10.1002/chem.202502141</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.202502141" target="_blank" >10.1002/chem.202502141</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Redox Cycling at Tellurium: Selective and Multiple Activation of Si―H Bonds in Common Organosilanes and SiH4

Popis výsledku v původním jazyce

Redox catalysis involving the tellurenyl triflate [2-(tBuNCH)C 6 H 4 Te][OTf ] was utilized for the activation of the common silanes Et3SiH, Ph 4–nSiHn (n = 1–3) as well as the difficult-to-handle gaseous SiH4 . Furthermore, complex siloxanes containing multiple Si─H bonds were converted into siloxylatedphenols, which are of high interest for the chemical industry. Insights into the catalytic cycle utilizing para-quinones asboth 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.

Název v anglickém jazyce

Redox Cycling at Tellurium: Selective and Multiple Activation of Si―H Bonds in Common Organosilanes and SiH4

Popis výsledku anglicky

Redox catalysis involving the tellurenyl triflate [2-(tBuNCH)C 6 H 4 Te][OTf ] was utilized for the activation of the common silanes Et3SiH, Ph 4–nSiHn (n = 1–3) as well as the difficult-to-handle gaseous SiH4 . Furthermore, complex siloxanes containing multiple Si─H bonds were converted into siloxylatedphenols, which are of high interest for the chemical industry. Insights into the catalytic cycle utilizing para-quinones asboth 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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA22-17230S" target="_blank" >GA22-17230S: Organokovové kationty telluru pro aktivaci E-H vazeb v boranech, silanech a fosfinech.</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

1521-3765

Svazek periodika

31

Číslo periodika v rámci svazku

43

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

9

Strana od-do

"e202502141"

Kód UT WoS článku

001524506900001

EID výsledku v databázi Scopus

2-s2.0-105010170034