Polysulfonylamine XXXV. Synthese, Roentgenstrukturanalysen und hochaufgeloeste Festkoerper-NMR-Spektren der ionischen Organozinn(IV)-dimesylamide und 2

Article abstract of DOI:10.1016/0022-328X(92)85075-8

(4) was prepared by treating Me3SnN(SO2Me)2 (1) with liquid ammonia; single crystals suitable for X-ray diffraction were grown from a solution in liquid ammonia by slow evaporation of the solvent at -42 deg C. 2 (5) was obtained from dimethyl sulfoxide and Me2Sn2 or 1 in refluxing CCl4, the co-product in the latter case being SnMe4.The crystallographic data at -95 deg C are for 4: monoclinic, space group P2₁/c, a 650.3(2), b 1464.7(3), c 1479.6(4) pm, β 94.63(2) deg, U 1.4046 nm³, Z=4; for 5: triclinic, space group P<*>, a 818.3(2), b 986.6(2), c 1119.9(3) pm, α 79.10(2), β 77.51(2), γ 77.58(2) deg, U 0.8524 nm³, Z=1.The structure refinement of 4 was based on 3092 reflections with F>4?(F) to give R=0.018.For 5, refinement using 3579 reflections with F>4?(F) yielded R=0.021.The crystals of both compounds consist of discrete (MeSO2)2N^- anions and Me3Sn(NH3)2⁺ or Me2Sn(DMSO)4²⁺ cations, respectively.The structures of the anions are similar to those observed in other ionic dimesylamides.In the cation of 4, the tin atom has an axially distorted trigonal-bipyramidal environment with apical NH3 molecules (Sn-N 232.8 and 238.3, Sn-C 211.7-212.4 pm, N-Sn-N 179.2, C-Sn-C 118.1-122.1, N-Sn-C 88.0-91.3 deg).The tin atom in the centrosymmetric cation of 5 displays trans-octahedral geometry with four DMSO molecules bonded through their oxygen atoms (Sn-C 211.4, Sn-O 219.9 and 221.4 pm, (O-Sn-O)_cis 88.9 and 91.1, O-Sn-C 86.8-93.2 deg).The oxygen centres of the sulfoxide ligands are sp²-hybridized with Sn-O-S 121.8 and 123.1 deg, S-O 154.4 and 155.4 pm. 5 is the first example of a structurally characterized tin(IV)-sulfoxide complex in which four sulfoxide ligands are coordinated to a single tin centre. 13C, 15N and 119Sn CP/MAS NMR spectra of solid 4 and 5 agree very well with the X-ray diffraction results.In both cases, the isotropic 119Sn chemical shifts and their tensorial properties support the nearest-neighbours-environment as shown by crystallography.The slight inequivalences of the NH3 and DMSO ligands, respectively, are mirrored in the 15N and 13C CP/MASS spectra of 4 and 5.The 119Sn CP/MAS spectrum of 4 is complicated by the simultaneous presence of scalar and quadrupolar coupling of two inequivalent 14N nuclei with 119Sn.