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

A set of -coordinated tellurium(II) compounds containing either C,N-chelating ligands CNR (where CN = 2-(RNCH)CH, R = Bu or Dipp; Dipp = 2,6-iPrCH) or N,C,N pincer ligands NCNR (where NCN = 2,6-(RNCH)CH, R = Bu or Dipp) were synthesized. In the case of C,N-chelated compounds, the reaction of CNDippLi with Te(dtc) (where dtc = EtNCS) 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) surprisingly furnished ionic bromides [NCNRTe]Br as a result of the exchange of dtc by Br coming from BuBr present in the reaction mixture. Furthermore, the reaction of CNDippTeCl or [NCNRTe]Br with silver salts AgX (X = OTf or SbF) 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 SOCl 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 SOCl 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 Te 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 EtPO 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.