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N-Coordinated tellurenium(ii) and telluronium(iv) cations: synthesis, structure and hydrolysis
Authors: Hejda Martin | Doležal Lukáš | Blahut Jan | Hupf Emanuel | Tydlitát Jiří | Jambor Roman | Růžička Aleš | Beckmann Jens | Dostál Libor
Year: 2023
Type of publication: článek v odborném periodiku
Name of source: Dalton Transactions
Publisher name: Royal Society of Chemistry
Place: Cambridge
Page from-to: 16235-16248
Titles:
Language Name Abstract Keywords
cze N-koordinované kationty telurenia (ii) a teluronia (iv): syntéza, struktura a hydrolýza Sada N-koordinovaných sloučenin teluru(ii) obsahující buď C,N- nebo N,C,N-chelatační ligandy byly syntetizovány. Byly studovány oxidace a hydrolýzy těchto sloučenin. N-koordinované; kationty; telurenia; teluronia; hydrolýza
eng N-Coordinated tellurenium(ii) and telluronium(iv) cations: synthesis, structure and hydrolysis A set of N-coordinated tellurium(ii) compounds containing either C,N-chelating ligands CN (R) (where CN = 2-(RN = CH)C6H4, R = tBu or Dipp; Dipp = 2,6-iPr(2)C(6)H(3)) or N,C,N pincer ligands NCN (R) (where NCN = 2,6-(RNCH)(2)C6H4, R = tBu or Dipp) were synthesized. In the case of C,N-chelated compounds, the reaction of (CNLi)-Li-Dipp with Te(dtc)2 (where dtc = Et2NCS2) in a 1 : 1 molar ratio smoothly provided the carbamate (CNTe)-Te-Dipp(dtc) which upon treatment with 2 eq. of HCl provided the chloride CNDippTeCl. In contrast, the analogous conversion of NCN (R) Li with Te(dtc)2 surprisingly furnished ionic bromides [NCN (R) Te]Br as a result of the exchange of dtc by Br coming from nBuBr present in the reaction mixture. Furthermore, the reaction of (CNTeCl)-Te-Dipp or [NCNRTe]Br with silver salts AgX (X = OTf or SbF6) provided the expected tellurenium cations [(CNTe)-Te-Dipp]SbF6 and [NCN (R) Te]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 [(CNTeCl2)-Te-tBu]X and [(NCNTeCl2)-Te-tBu]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 [(CNTeCl2)-Te-Dipp]SbF6 and [(NCNTeCl2)-Te-Dipp]SbF6, which could solely be characterized in solution. Compounds [(CNTeCl2)-Te-tBu]OTf and [(NCNTeCl2)-Te-tBu]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 Te-125 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. N-Coordinated; tellurenium; telluronium; cations; hydrolysis

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