123798-55-0Relevant academic research and scientific papers
Base-catalyzed nitrito to nitro linkage isomerization of cobalt(III), rhodium(III), and iridium(III) pentaammine complexes
Jackson, W. Gregory,Lawrance, Geoffrey A.,Lay, Peter A.,Sargeson, Alan M.
, p. 904 - 910 (1980)
The nitrito ions [M(NH3)5(ONO)]2+ (M = Co(III), Rh(III), or Ir(III)) rearrange to their nitro forms [M(NH3)5(NO2)]2+ in aqueous base according to the rate law kobsd = ks + kOH[OH-] where at μ = 1.0 M, 25.0°C: ks = 6.9 (±0.2) × 10-5 s-1, ΔHs≠ = 95 ± 4 kJ mol-1, ΔSs≠ = -4 ± 12 J K-1 mol-1, kOH = 5.9 (±0.2) × 10-3 dm3 mol-1 s-1, ΔHOH≠ = 110 ± 1 kJ mol-1, ΔSOH≠ = +82 ± 4 J K-1 mol-1, M = Co; ks = 9.6 (±0.2) × 10-4 s-1, ΔHs≠ = 85 ± 2.5 kJ mol-1, ΔSx≠ = -18 ± 9 J K-1 mol-1, kOH = 7.6 (±0.2) × 10-3 dm3 mol-1 s-1, ΔHOH≠ = 96 ± 2 kJ mol-1, ΔSOH≠ = +38 ± 6 J K-1 mol-1, M = Rh; ks = 3.0 (±0.1) × 10-5 s-1, ΔHs≠ = 94 ± 2 kJ mol-1, = 16 ± 5 J K-1 mol-1, kOH = 2.7 (±0.1) × 10-5 dm3 mol-1 s-1, ΔHOH≠ = 109 ± 2 kJ mol-1, ΔSOH≠ = 34 ± 6 J K-1 mol-1, M = Ir. For the cobalt complex the pressure dependence of kOH (ΔV≠ = +27 (±1.4) cm3 mol-1, Δβ≠ = 5 (±2) cm-3 kbar-1 mol-1) points to a conjugate base preequilibrium for the base-catalyzed path. The metal ion dependence of kOH/ks (95:9:1 for Co:Rh:lr) is also consistent with a conjugate base process. [Co(NH3)5(ONO)]2+ rearranges to [Co(NH3)5(NO2)]2+ without exchange of oxygen with H218O, 18OH-, or free N18O2- (1 M); both the ks and kOH paths are intramolecular. Up to 1 M OH there is 3)5(OH)]2+. Both rate constants ks and kOH for M = Co decrease with increasing ionic strength (25°C, 105ks = 6.9, 7.4, 103kOH = 5.9, 14.5; μ = 1.0, 0.1, respectively). cis- and trans-[Co(en)2(ONO)2]+ and [Co(en)2(ONO)(NO2)]+ rearrange by both pathways to the dinitro complexes without change in configuration, and (+)cis-[Co(en)2(ONO)(NO2)]+ rearranges without loss of chirality. For the kOH reaction these results also differ from the normal substitution chemistry where there is some steric change. In addition to the O to N rearrangement, a much faster O to O scrambling process has been identified for the cobalt complex using 18O tracers.
Hydroxylamine as an oxygen nucleophile: Substitution of sulfonamide by a hydroxyl group in benzothiazole-2-sulfonamides
Kamps, Jos J. A. G.,Belle, Roman,Mecinovi?, Jasmin
supporting information, p. 1103 - 1108 (2013/03/28)
Benzothiazole-2-sulfonamides react with an excess of hydroxylamine in aqueous solutions to form 2-hydroxybenzothiazole, sulfur dioxide, and the corresponding amine. Mechanistic studies that employ a combination of structure-reactivity relationships, oxygen labeling experiments, and (in)direct detection of intermediates and products reveal that the reaction proceeds via oxygen attack, and that oxygen incorporated in the 2-hydroxybenzothiazole product derives from hydroxylamine. The reaction, which is performed under mild conditions, can be used as a deprotection method for cleavage of benzothiazole-2-sulfonyl-protected amino acids.
