Two-electron oxidation of the [N(PiPr(2)E)(2)](-) anion with iodine produces the cyclic [N(PiPr(2)E)(2)](+) (E = Se, Te) cations, which exhibit long E-E bonds in the iodide salts [N((PPr2Se)-Pr-i)(2)]I (4) and [N((PPr2Te)-Pr-i)(2)]I (5). The iodide salts 4 and 5 are converted to the ion-separated salts [N((PPr2Se)-Pr-i)(2)]SbF6 (6) and [N((PPr2Te)-Pr-i)(2)] SbF6 (7) upon treatment with AgSbF6. Compounds 4-7 were characterized in solution by multinuclear NMR, vibrational, and UV-visible spectroscopy supported by DFT calculations. A structural comparison of salts 4-7 and [N((PPr2Te)-Pr-i)(2)] Cl (8) confirms that the long E-E bonds in 4, 5, and 8 can be attributed primarily to the donation of electron density from a lone pair of the halide counterion into the E-E sigma* orbital (LUMO) of the cation. The phenyl derivative [N(PPh2Te)(2)]I (9) was prepared in a similar manner. However, the attempted synthesis of the selenium analogue, [N(PPh2Se)(2)]I, produced a 1:1 mixture of [N(PPh2Se)(2)(mu-Se)][I] (10) and [SeP(Ph-2)N(Ph-2)PI] (11). DFT calculations of the formation energies of 10 and 11 support the observed decomposition. Compound 10 is a centrosymmetric dimer in which two six-membered NP2Se3 rings are bridged by two I- anions. Compound 11 produces the nine-atom chain {[N(PPh2)(2)Se] (2)(mu-O)} (12) upon hydrolysis during crystallization. The reaction between [(TMEDA)NaN(PiPr(2)Se)(2)] and SeCl2 in a 1:1 molar ratio yields the related acyclic species [SeP(Pr-i(2)) N(Pr-i(2)) PCl] (13), which was characterized by multinuclear NMR spectroscopy and an X-ray structural determination.