Reaction products of diorganotin(IV) oxides, [R.sub.2]SnO, with nitric acid. Part 2--R = n-butyl and t-butyl

The reaction of diorganotin(IV) oxides, [R.sub.2]SnO 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-[Bu.sub.2]Sn[(N[O.sub.3]).sub.2] x 2[H.sub.2]O (2d) and t-[Bu.sub.2]Sn[(N[O.sub.3]).sub.2] x 2[H.sub.2]O (2e), the mixed diorganotin(IV) nitrate methoxide oxide n-[Bu.sub.2]Sn(N[O.sub.3]) (n-[Bu.sub.2]SnOMe)O (6), and the diorganotin(IV) nitrate hydroxide hydrate t-[Bu.sub.2]Sn(N[O.sub.3])(OH)-[H.sub.2]O = [t-[Bu.sub.2]Sn(OH)([H.sub.2]O)][N[O.sub.3]] (7). On examination of the solubility of the primary reaction products in different solvents, the three additional compounds t-[Bu.sub.2]Sn(N[O.sub.3])(OH) x DMSO (8), t-[Bu.sub.2]Sn(N[O.sub.3])(OH) x THF, and 2-t-[Bu.sub.2]Sn(N[O.sub.3])(OH) x DMF = [[t-[Bu.sub.2]Sn(OH)dmf].sub.2][[N[O.sub.3]].sub.2] x[[t-[Bu.sub.2]Sn(N[O.sub.3])OH].sub.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. Key words: diorganotin(IV) compounds, nitrates, tetraorganodistannoxanes, hydrates, structure types, structure determination, coordination behaviour. La reaction des oxydes de diorganoetain(IV), de formule [R.sub.2]SnO (ou R = n-Butyl et t-Butyl), avec l'acide nitrique, dans diverses proportions strechiometriques a conduit a la formation de differents produits dont la nature dependait des groupes organiques lies a l'atome d'etain : les dinitrates de diorganetain(IV) dihydrates, n[Bu.sub.2]Sn[(N[O.sub.3]).sub.2] x 2[H.sub.2]O (2d) et t[Bu.sub.2]Sn[(N[O.sub.3]).sub.2] x 2[H.sub.2]O (2e), le compose mixte d'oxyde methanolate de diorganoetain(IV) et nitrate de diorganoetain(IV), n[Bu.sub.2]Sn(N[O.sub.3])(n[Bu.sub.2]SnOMe)O (6) et l'hydroxyde nitrate de diorganoetain(IV) hydrate, t[Bu.sub.2]Sn(N[O.sub.3])(OH)-[H.sub.2]O = [t[Bu.sub.2]Sn(OH)([H.sub.2]O)][N[O.sub.3]] (7). Apres examen de la solubilite des produits primaires de reaction dans differents solvants, trois autres composes ont pu etre isoles : t[Bu.sub.2]Sn(N[O.sub.3])(OH) x DMSO (8), t[Bu.sub.2]Sn(N[O.sub.3])(OH) x THF et 2t[Bu.sub.2]Sn(N[O.sub.3])(OH)-DMF = [t[Bu.sub.2]Sn(OH)dmf]2[[N[O.sub.3]].sub.2] x[[t[Bu.sub.2]Sn(N[O.sub.3])OH].sub.2] (9). La structure de ces composes aete determinee par cristallographie aux rayons X (premiers resultats obtenus pour 7), en particulier la dimensionnalite (2d et 2c = molecules monomeriques a liaisons hydrogenes, 6 = molecules dimeriques de structure en echelle; 7 = cation dimerique, 8 = molecule dimerique associeea des molecules de solvant a liaisons hydrogene; 9 = deux composants dimeriques), la coordination de l'etain (6, 7, 8, 9 = trigonalebipyramidale; 2d, 2e = ti huit plis) et les modes de liaisons du nitrate (7, 9 = isole, a liaisons hydrogene; monodentate, avec les composants dimeriques 6, 8 et 9; bidentate symetrique, avec 2d et 2e), le compose 9 ayant ete analyse a l'aide des longueurs des liaisons Sn-O et N-O. [Traduit par la Redaction] Mots-cles : diorganoetains(IV), nitrates, tetraorganodistannoxanes, hydrates, types de structure, determination de la structure, comportement de coordination.
Introduction Nitrates with diorganotin(IV) moieties [R.sub.2]Sn belong to the longest known compounds in organotin(IV) chemistry, (1,2) prepared by the reaction of diorganotin(IV) oxides with nitric acid. When the silver nitrate [...]