Selective oxidation and functionalization of 6‑diphenylphosphinoacenaphthyl-5-tellurenyl species 6‑Ph₂P‑Ace-5-TeX (X = Mes, Cl, O₃SCF₃). Various types of P−E···Te(II,IV) bonding situations (E = O, S, Se)

The syntheses of the diaryltelluride 6-Ph₂P(O)-Ace-5-TeMes (1O), the tellurenyl(II) chlorides 6-Ph₂P(E)-Ace-5-TeCl (2O, E = O; 2S, E = S; 2Se, E = Se), the ditelluroxonium(IV) bis(triflate) [6-Ph₂P(O)-Ace-5-TeO]₂(O₃SCF₃)₂ (3O), the diaryltellurium(IV) dichloride 6-Ph₂P(O)-Ace-5-TeMesCl₂ (4O), the diarylhalotelluronium(IV) polyhalides [6-Ph₂P(O)-Ace-5-TeMesBr]Br₃ (5O) and [6-Ph₂P(O)-Ace-5-TeMesI]₂I₈ (6O), and the aryltellurium(IV) trihalides 6-Ph₂P(O)-Ace-5-TeX₃ (7O, X = Cl; 8O, X = Br; 9O, X = I) are reported. All compounds have been characterized experimentally by means of multinuclear NMR spectroscopy as well as single-crystal X-ray crystallography. The diverse P–E···Te bonding situations (E = O, S, Se) in the peri region have also been investigated in detail by complementary DFT studies including the calculation of peri interaction energies (α-PIE) as well as topological analyses of the electron and pair densities according to the AIM and ELI-D space-partitioning schemes and evaluation of noncovalent bonding aspects applying the NCI index. To illustrate the different bond situations, appropriate Lewis formula representations have been suggested.