N-Coordinated tellurenium(II) and telluronium(IV) cations: synthesis, structure and hydrolysis

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F23%3A00578070" target="_blank" >RIV/61388963:_____/23:00578070 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216275:25310/23:39920979

Výsledek na webu

<a href="https://doi.org/10.1039/D3DT02404K" target="_blank" >https://doi.org/10.1039/D3DT02404K</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d3dt02404k" target="_blank" >10.1039/d3dt02404k</a>

Jazyk výsledku

angličtina

Název v původním jazyce

N-Coordinated tellurenium(II) and telluronium(IV) cations: synthesis, structure and hydrolysis

Popis výsledku v původním jazyce

A set of N-coordinated tellurium(II) compounds containing either C,N-chelating ligands CNR (where CN = 2-(RN[double bond, length as m-dash]CH)C6H4, R = tBu or Dipp, Dipp = 2,6-iPr2C6H3) or N,C,N pincer ligands NCNR (where NCN = 2,6-(RN[double bond, length as m-dash]CH)2C6H4, R = tBu or Dipp) were synthesized. In the case of C,N-chelated compounds, the reaction of CNDippLi with Te(dtc)2 (where dtc = Et2NCS2) in a 1 : 1 molar ratio smoothly provided the carbamate CNDippTe(dtc) which upon treatment with 2 eq. of HCl provided the chloride CNDippTeCl. In contrast, the analogous conversion of NCNRLi with Te(dtc)2 surprisingly furnished ionic bromides [NCNRTe]Br as a result of the exchange of dtc by Br coming from nBuBr present in the reaction mixture. Furthermore, the reaction of CNDippTeCl or [NCNRTe]Br with silver salts AgX (X = OTf or SbF6) provided the expected tellurenium cations [CNDippTe]SbF6 and [NCNRTe]X. To further increase the Lewis acidity of the central atom, the oxidation of selected compounds with 1 eq. of SO2Cl2 was examined yielding stable compounds [CNtBuTeCl2]X and [NCNtBuTeCl2]X. The oxidation of the Dipp substituted compounds proved to be more challenging and an excess of SO2Cl2 was necessary to obtain the oxidized products [CNDippTeCl2]SbF6 and [NCNDippTeCl2]SbF6, which could solely be characterized in solution. Compounds [CNtBuTeCl2]OTf and [NCNtBuTeCl2]OTf were shown to undergo a controlled hydrolysis to the corresponding telluroxanes. All compounds were studied by multinuclear NMR spectroscopy in solution and for selected compounds solid state 125Te NMR spectroscopy and single-crystal X-ray diffraction analysis were performed. The Lewis acidity of the studied cations was examined by the Gutmann–Beckett method using Et3PO as the probing agent. The Te–N chalcogen bonding situation of selected compounds has also been examined computationally by a set of real-space bonding indicators.

Název v anglickém jazyce

N-Coordinated tellurenium(II) and telluronium(IV) cations: synthesis, structure and hydrolysis

Popis výsledku anglicky

A set of N-coordinated tellurium(II) compounds containing either C,N-chelating ligands CNR (where CN = 2-(RN[double bond, length as m-dash]CH)C6H4, R = tBu or Dipp, Dipp = 2,6-iPr2C6H3) or N,C,N pincer ligands NCNR (where NCN = 2,6-(RN[double bond, length as m-dash]CH)2C6H4, R = tBu or Dipp) were synthesized. In the case of C,N-chelated compounds, the reaction of CNDippLi with Te(dtc)2 (where dtc = Et2NCS2) in a 1 : 1 molar ratio smoothly provided the carbamate CNDippTe(dtc) which upon treatment with 2 eq. of HCl provided the chloride CNDippTeCl. In contrast, the analogous conversion of NCNRLi with Te(dtc)2 surprisingly furnished ionic bromides [NCNRTe]Br as a result of the exchange of dtc by Br coming from nBuBr present in the reaction mixture. Furthermore, the reaction of CNDippTeCl or [NCNRTe]Br with silver salts AgX (X = OTf or SbF6) provided the expected tellurenium cations [CNDippTe]SbF6 and [NCNRTe]X. To further increase the Lewis acidity of the central atom, the oxidation of selected compounds with 1 eq. of SO2Cl2 was examined yielding stable compounds [CNtBuTeCl2]X and [NCNtBuTeCl2]X. The oxidation of the Dipp substituted compounds proved to be more challenging and an excess of SO2Cl2 was necessary to obtain the oxidized products [CNDippTeCl2]SbF6 and [NCNDippTeCl2]SbF6, which could solely be characterized in solution. Compounds [CNtBuTeCl2]OTf and [NCNtBuTeCl2]OTf were shown to undergo a controlled hydrolysis to the corresponding telluroxanes. All compounds were studied by multinuclear NMR spectroscopy in solution and for selected compounds solid state 125Te NMR spectroscopy and single-crystal X-ray diffraction analysis were performed. The Lewis acidity of the studied cations was examined by the Gutmann–Beckett method using Et3PO as the probing agent. The Te–N chalcogen bonding situation of selected compounds has also been examined computationally by a set of real-space bonding indicators.

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

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

52

Číslo periodika v rámci svazku

44

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

14

Strana od-do

16235-16248

Kód UT WoS článku

001085736400001

EID výsledku v databázi Scopus

2-s2.0-85175434143