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 CNR (where CN = 2-(RNCH)C 6 H 4 , R = t Bu or Dipp; Dipp = 2,6-iPr 2 C 6 H 3 ) or N,C,N pincer ligands NCNR (where NCN = 2,6-(RNCH) 2 C 6 H 4 , R = t Bu or Dipp) were synthesized. In the case of C,N-chelated compounds, the reaction of CNDippLi with Te(dtc) 2 (where dtc = Et 2 NCS 2 ) 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 n BuBr present in the reaction mixture. Furthermore, the reaction of CNDippTeCl or [NCNRTe]Br with silver salts AgX (X = OTf or SbF 6 ) 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 SO 2 Cl 2 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 SO 2 Cl 2 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 125 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 Et 3 PO 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.