title: Synthesis and characterization of the SO(2)N(3)(-), (SO(2))(2)N(3)(-), and SO(3)N(3)(-) anions.
abstract: SO(2) solutions of azide anions are bright yellow, and their Raman spectra indicate the presence of covalently bound azide. Removal of the solvent at -64 degrees C from CsN(3) or N(CH(3))(4)N(3) solutions produces yellow (SO(2))(2)N(3)(-) salts. Above -64 degrees C, these salts lose 1 mol of SO(2), resulting in white SO(2)N(3)(-) salts that are marginally stable at room temperature and thermally decompose to the corresponding azides and SO(2). These anions were characterized by vibrational and (14)N NMR spectroscopy and theoretical calculations. Slow loss of the solvent by diffusion through the walls of a sealed Teflon tube containing a sample of CsSO(2)N(3) in SO(2) resulted in white and yellowish single crystals that were identified by X-ray diffraction as CsSO(2)N(3).CsSO(3)N(3) with a = 9.542(2) A, b = 6.2189(14) A, c = 10.342(2) A, and beta = 114.958(4) degrees in the monoclinic space group P2(1)/m, Z = 2, and Cs(2)S(2)O(5).Cs(2)S(2)O(7).SO(2), respectively. Pure CsSO(3)N(3) was also prepared and characterized by vibrational spectroscopy. The S-N bond in SO(2)N(3)(-) is much weaker than that in SO(3)N(3)(-), resulting in decreased thermal stability, an increase in the S-N bond distance by 0.23 A, and an increased tendency to undergo rotational disorder. This marked difference is due to SO(3) being a much stronger Lewis acid (pF(-) value of 7.83) than SO(2) (pF(-) value of 3.99), thus forming a stronger S-N bond with the Lewis base N(3)(-). The geometry of the free gaseous SO(2)N(3)(-) anion was calculated at the RHF, MP2, B3LYP, and CCSD(T) levels. The results show that only the correlated methods correctly reproduce the experimentally observed orientation of the SO(2) group.
authors.affiliation: Propulsion Sciences and Advanced Concepts Division, Air Force Research Laboratory (AFRL/PRS), Edwards AFB, California 93524, USA. karl.christe@edwards.af.mil
authors.forename: Karl O
authors.initials: KO
authors.lastname: Christe
authors.forename: Jerry A
authors.initials: JA
authors.lastname: Boatz
authors.forename: Michael
authors.initials: M
authors.lastname: Gerken
authors.forename: Ralf
authors.initials: R
authors.lastname: Haiges
authors.forename: Stefan
authors.initials: S
authors.lastname: Schneider
authors.forename: Thorsten
authors.initials: T
authors.lastname: Schroer
authors.forename: Fook S
authors.initials: FS
authors.lastname: Tham
authors.forename: Ashwani
authors.initials: A
authors.lastname: Vij
authors.forename: Vandana
authors.initials: V
authors.lastname: Vij
authors.forename: Ross I
authors.initials: RI
authors.lastname: Wagner
authors.forename: William W
authors.initials: WW
authors.lastname: Wilson