Reaction products of diorganotin(IV) oxides, R₂SnO, with nitric acid. Part 1: R = methyl, ethyl, and isopropyl

Abstract

The reaction of diorganotin(IV) oxides, R 2 SnO with R = Me, Et, and i-Pr, with nitric acid in different stoichiometric ratios resulted in the formation of different products depending on the organic groups. The diorganotin(IV) nitrate hydroxides Me 2 Sn(NO 3 )(OH) (1a) Et 2 Sn(NO 3 )(OH), ␣-1b, ␤-1b, i-Pr 2 Sn(NO 3 )(OH) (1c), the diisopropyltin(IV) dinitrate dihydrate, i-Pr 2 Sn(NO 3 ) 2 ·2H 2 O (2c) and the diisopropyltin(IV) nitrate oxalate dihydrate, [i-Pr 2 Sn(NO 3 )] 2 Ox·2H 2 O (3) as side-product. On examination of the solubility of the primary reaction products in different solvents, the two additional compounds Me 2 Sn(NO 3 )(OH)·DMSO (4) and 2i-Pr 2 Sn(NO 3 ) 2 ·3DMSO = [i-Pr 2 Sn(NO 3 )(dmso) 3 ] [i-Pr 2 Sn(NO 3 ) 3 ] (5) have been isolated. All compounds have been structurally characterized by single crystal X-ray diffraction with special respect to dimensionality (1a, ␣-1b, 1c = dimeric molecules hydrogen bonded to one-dimensional chains; ␤-1b = two-dimensional coordination polymer; 2c = monomeric; 3 = monomeric, tin atoms linked via a double side-on chelating oxalate ion; 4 = dimeric, 5 = monomeric anion/cation), tin coordination (trigonalbipyramidal = 1a, ␣-1b, 1c; six-fold = ␤-1b; seven-fold = 3, 4, 5-cation; eight-fold = 2c, 5-anion) and nitrate bonding modes (monodentate = 1a, ␣-1b, 1c; unsymmetrical bidentate = 3, symmetrical bidentate = 3, 4, 5-cation, 5-anion; syn-anti bridging = ␤-1b), the latter one being analysed using both, Sn-O and N-O distances.Résumé : La réaction des oxydes de diorganoétain(IV) oxides, R 2 SnO (où R=Me, Et et i-Pr), avec l'acide numériques dans diverses proportions stoechiométriques a conduit à la formation de différents produits dont la nature dépendait des groupes organiques : les hydroxydes nitrate de diorganoétain(IV), de formules Me 2 Sn(NO 3 )(OH) (1a), Et 2 Sn(NO 3 )(OH) (á-1b et â-1b) et i-Pr 2 Sn(NO 3 )(OH) (1c), le dinitrate de diisopropylétain(IV) dihydraté, i-Pr 2 Sn(NO 3 ) 2 ·2H 2 O (2c), et un sous-produit, l'oxalate nitrate de diisopropylétain(IV) dihydraté, [i-Pr 2 Sn(NO 3 )] 2 Ox·2H 2 O (3). Après examen de la solubilité des produits primaires de réaction dans différents solvants, deux autres composés ont été isolés : Me 2 Sn(NO 3 )(OH)·DMSO (4) et 2i-Pr 2 Sn(NO 3 ) 2 ·3DMSO = [i-Pr 2 Sn(NO 3 )(dmso) 3 ] [i-Pr 2 Sn(NO 3 ) 3 ] (5). La structure de ces composés a été déterminée par cristallographie aux rayons X, en particulier la dimensionnalité (1a, á-1b, 1c = molécules dimériques reliées par liaisons hydrogène à des chaînes unidimensionnelles; â-1b = polymère de coordination bidimensionnel; 2c = monomère; 3 = monomère; atomes d'étain reliés par l'intermédiaire d'un ion double latéral d'oxalate chélateur; 4 = dimère, 5 = anion ou cation monomérique), coordination de l'étain (trigonale-bipyramidale, avec 1a, á-1b, 1c; à six plis, avec â-1b; à sept plis, avec 3, 4 et le cation 5; à huit plis, avec 2c et l'anion 5) et les modes de liaisons du nitrate (monodentate, avec 1a, á-1b et 1c; bidentate asymétrique, avec 3, bidentate symétrique, avec 3, 4, le ca...

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

“…In the case of the two organic groups, R = n-butyl and t-butyl, studied in this second part, a molar ratio of 1:1 between the oxide and nitric acid resulted in the formation of two unprecedented compounds: the nitrate hydroxide hydrate R 2 Sn(NO 3 )(OH)·H 2 O (7) for R = t-Bu and the mixed nitrate methoxide tetraorganodistannoxane (R 2 SnNO 3 )(R 2 SnOMe)O (6) for R = n-Bu. Using a large excess of acid resulted, in both cases (R = n-Bu and t-Bu), in the formation of a dinitrate dihydrate, R 2 Sn(NO 3 ) 2 ·2H 2 O (2d for R = n-Bu and 2e for R = t-Bu), already known from 2c with R = i-Pr (Part 1 18 ). Limitations of the reaction conditions chosen were found in the case of R = t-Bu because too few crystals of the oxalate (t-Bu 2 SnOx) were found in all samples of the primary reaction products.…”

“…When including the results of Part 1, 18 we can ascertain two trends. (i) Smaller organic groups (Me and Et) prefer the formation of pure diorganotin(IV) hydroxide nitrates instead of diorganotin(IV) dinitrate hydrates under all conditions applied, whereas larger ones (n-Bu and t-Bu) favour the formation of diorganotin(IV) dinitrate hydrates when using a large excess of nitric acid.…”

“…1) exhibits, in principle, the same molecular structure with an eightfold, hexagonal-bipyramidal coordination at tin as the corresponding isopropyl compound i-Pr 2 Sn(NO 3 ) 2 ·2H 2 O (2c, Part 1 18 ). 2d differs from the latter, however, first in that the molecule belongs to point group C i with the tin atom lying on a crystallographic center of symmetry, and second in relation to the coordination mode of the nitrate ion, which coordinates to the tin atom more symmetrically (2d: Tables 3 and 4 of Part 1 18 in the case of symmetrical chelating nitrate groups.…”

“…18 Details of crystal data, data collection, and structure refinement are summarized in Table 1. Additional crystallographic data can be found in the Supplementary data.…”