⁷⁷Se NMR Spectroscopic, DFT MO, and VBT Investigations of the Reversible Dissociation of Solid (Se₆I₂)[AsF₆]₂·2SO₂in Liquid SO₂to Solutions Containing 1,4-Se₆I₂²⁺in Equilibrium with Se_<i>n</i>²⁺(<i>n</i>= 4, 8, 10) and Seven Binary Selenium Iodine Cations: Preliminary Evidence for 1,1,4,4-Se₄Br₄²⁺and<i>cyclo</i>-Se₇Br⁺

The composition of a complex equilibrium mixture formed upon dissolution of (Se(6)I(2))[AsF(6)](2).2SO(2) in SO(2)(l) was studied by (77)Se NMR spectroscopy at -70 degrees C with both natural-abundance and enriched (77)Se-isotope samples (enrichment 92%). Both the natural-abundance and enriched NMR spectra showed the presence of previously known cations 1,4-Se(6)I(2)(2+), SeI(3)(+), 1,1,4,4-Se(4)I(4)(2+), Se(10)(2+), Se(8)(2+), and Se(4)(2+). The structure and bonding in 1,4-Se(6)I(2)(2+) and 1,1,4,4-Se(4)I(4)(2+) were explored using DFT calculations. It was shown that the observed Se-Se bond alternation and presence of thermodynamically stable 4ppi-4ppi Se-Se and 4ppi-5ppi Se-I bonds arise from positive charge delocalization from the formally positively charged tricoordinate Se(+). The (77)Se chemical shifts for cations were calculated using the relativistic zeroth-order regular approximation (ZORA). In addition, calculations adding a small number of explicit solvent molecules and an implicit conductor-like screening model were conducted to include the effect that solvent has on the chemical shifts. The calculations yielded reasonable agreement with experimental chemical shifts, and inclusion of solvent effects was shown to improve the agreement over vacuum values. The (77)Se NMR spectrum of the equilibrium solution showed 22 additional resonances. These were assigned on the basis of (77)Se-(77)Se correlation spectroscopy, selective irradiation experiments, and spectral simulation. By combining this information with the trends in the chemical shifts, with iodine, selenium, and charge balances, as well as with ZORA chemical shift predictions, these resonances were assigned to acyclic 1,1,2-Se(2)I(3)(+), 1,1,6,6-Se(6)I(4)(2+), and 1,1,6-Se(6)I(3)(+), as well as to cyclic Se(7)I(+) and (4-Se(7)I)(2)I(3+). A preliminary natural-abundance (77)Se NMR study of the soluble products of the reaction of (Se(4))[AsF(6)](2) and bromine in liquid SO(2) included resonances attributable to 1,1,4,4-Se(4)Br(4)(2+)(.) These assignments are supported by the agreement of the observed and calculated (77)Se chemical shifts. Resonances attributable to cyclic Se(7)Br(+) were also observed. The thermal stability of (Se(6)I(2))[AsF(6)](2).2SO(2)(s) was consistent with estimates of thermodynamic values obtained using volume-based thermodynamics (VBT) and the first application of the thermodynamic solvate difference rule for nonaqueous solvates. (Se(6)I(2))[AsF(6)](2).2SO(2)(s) is the first example of a SO(2) solvate for which the nonsolvated parent salt, (Se(6)I(2))[AsF(6)](2)(s), is not thermodynamically stable, disproportionating to Se(4)I(4)(AsF(6))(2)(s) and Se(8)(AsF(6))(2)(s) (DeltaG degrees for the disproportion reaction is estimated to be -17 +/- 15 kJ mol(-1) at 298 K from VBT theory).

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