Reaction products of diorganotin(IV) oxides, R2SnO, with nitric acid. Part 2 – R = n-butyl and t-butyl

Abstract

The reaction of diorganotin(IV) oxides, R2SnO with R = n-butyl and t-butyl, with nitric acid in different stoichiometric ratios resulted in the formation of different products depending on the organic groups attached to the tin atom: the diorganotin(IV) dinitrate dihydrates, n-Bu2Sn(NO3)2·2H2O (2d) and t-Bu2Sn(NO3)2·2H2O (2e), the mixed diorganotin(IV) nitrate methoxide oxide n-Bu2Sn(NO3)(n-Bu2SnOMe)O (6), and the diorganotin(IV) nitrate hydroxide hydrate t-Bu2Sn(NO3)(OH)·H2O = [t-Bu2Sn(OH)(H2O)][NO3] (7). On examination of the solubility of the primary reaction products in different solvents, the three additional compounds t-Bu2Sn(NO3)(OH)·DMSO (8), t-Bu2Sn(NO3)(OH)·THF, and 2-t-Bu2Sn(NO3)(OH)·DMF = [t-Bu2Sn(OH)dmf]2[NO3]2·[t-Bu2Sn(NO3)OH]2 (9) could be isolated. All compounds have been structurally characterized by single crystal X-ray diffraction (primary results for 7) with special attention paid to dimensionality (2d and 2c = monomeric, hydrogen bonded molecules; 6 = dimeric molecules of ladder-type structure; 7 = dimeric cation; 8 = dimeric molecule with hydrogen bonded solvent molecules; 9 = both components dimeric), tin coordination (6, 7, 8, and 9 = trigonal bipyramidal; 2d and 2e = eightfold), and nitrate bonding modes (7 and 9 = isolated, hydrogen bonded; 6, 8, and 9 (component 2) = monodentate; 2d and 2e = symmetrical bidentate), the latter one being analyzed using both Sn–O and N–O distances.