The previously known dimeric arylantimony oxides (Ph3SbO)2 and [2,6-(Me2NCH2)2C6H3SbO]2 were disaggregated by the Lewis acid B(C6F5)3 giving rise to the formation of the Lewis pair complexes Ph3SbOB(C6F5)3 and 2,6-(Me2NCH2)2C6H3SbOB(C6F5)3 having short bipolar single Sb-O bonds.

The syntheses of the diaryltelluride 6-Ph 2 P(O)-Ace-5-TeMes (1O), the tellurenyl(II) chlorides 6-Ph 2 P(E)-Ace-5-TeCl (2O, E = O; 2S, E = S; 2Se, E = Se), the ditelluroxonium(IV) bis(triflate) [6-Ph 2 P(O)-Ace-5-TeO] 2 (O 3 SCF 3 ) 2 (3O), the diaryltellurium(IV) dichloride 6-Ph 2 P(O)-Ace-5-TeMesCl 2 (4O), the diarylhalotelluronium(IV) polyhalides [6-Ph 2 P(O)-Ace-5-TeMesBr]Br 3 (5O) and [6-Ph 2 P(O)-Ace-5-TeMesI] 2 I 8 (6O), and the aryltellurium(IV) trihalides 6-Ph 2 P(O)-Ace-5-TeX 3 (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.