Preparative reactions for the ions Se2-, HSe- and [Se(x)]2- in protic and aprotic solvent systems are established, and these ions in solution have been characterized by the most informative probe, Se-77 NMR. Fully reduced solutions in DMF contain HSe- for which delta-Se ranges between -530 and -390 ppm (vs Me2Se) depending strongly on solvent and temperature: 1J(Se-H) = 26 Hz. Although HSe- and Se2- are in fast equilibrium, there is no direct NMR evidence for the conjugate strong base Se2- in any of these solutions, and it is predicted that delta-Se(Se2-) < -650 ppm. There is no NMR evidence for [Se2]2-, which is believed to disproportionate to HSe- plus [Se(x)]2- (x > 2) or Se(s). The polyselenide ions [Se(x)]2-, x = 3-6, all exist in DMF, and the resonances for all selenium atoms in each of these ions have been observed and assigned. Using alpha, beta, gamma to signify selenium positions relative to the equivalent ends of the chain, the delta-Se(alpha), delta-Se(beta), delta-Se(gamma) data [in DMF plus 38% (vol) EtOH, 230-degrees-K] are: [Se3]2-, 193, 214, -; [Se4]2-, 256, 581, -; [Se5]2-, 354, 570, 868; [Se6]2-, 404, 636, 807. The chemical shifts of the Se(alpha) in these ions are very responsive to the solvent proticity, becoming more negative in the range DMF --> ethanol, while the Se(beta) atoms respond much less, and the effect at the Se(gamma) atoms is small and can be in the other direction. Protic solvents retard the selenium exchange reactions of polyselenide ions. Comparative analysis is made of the delta-Se values for related compounds of type XSe- or with chains of selenium atoms. There is no NMR evidence for ions with x > 6. The spirocyclic ion [Se(Se5)2]2- is formed from [Se(x)]2- with many oxidants, including NO3- in DMF, and possesses only one exchanging Se-77 resonance at 720 ppm.
