56-35-9Relevant academic research and scientific papers
Reactivity behavior of (hydroxy)diorganotin(IV)methanesulfonates with ionic nucleophiles - Synthesis and structural characterization of novel diorganostannate salts, [R2Sn(μ-OH)(OSO2Me)(ONO 2)]22Bu4N
Shankar, Ravi,Kumar, Mukesh,Chadha, Raj K.,Narula, Suraj P.
, p. 71 - 75 (2004)
The reaction of R2Sn(OH)OSO2Me [R=n-Pr (1a), or n-Bu (1b)] with one equivalent of Bu4NNO3 in CH 2Cl2 proceeds via nucleophilic addition of NO 3- ion to the Lewis acidic tin center and results in the formation of novel diorganostannates, [R2Sn(μ-OH)(OSO 2Me)(ONO2)]22Bu4N [R=n-Pr (2a), n-Bu(2b)]. The molecular structure of 2b comprises of hydroxy-bridged dimer with monodentate methanesulfonate and nitrate groups bonded to each tin atom. Analogous reactions of the tin precursor, 1b with strong nucleophiles such as Bu4NX (X=F-, OAc-) and RLi (R=n-Bu, Me) favor ionic metathesis pathway involving Sn-OSO2Me bond cleavage. This approach provides a simple and facile synthetic route for triorganotin oxides, (R2R′Sn)2O (R=R′=n-Bu, R=n-Bu, R′=Me).
Unexpected Temperature-dependent Stereoselectivity in the Thermolysis of 2-Trialkylstannyl Alcohols
Jousseaume, B.,Noiret, N.,Pereyre, M.,Frances, J. M.
, p. 739 - 740 (1992)
Thermolysis of substituted 2-trialkylstannyl alcohols reveals a complete reversal of selectivity between 100 and 160 deg C i.e. an erythro 2-trialkylstannyl alcohol leads to an (E)-alkene at 100 deg C or a (Z)-alkene at 160 deg C; this unexpected result depends on the formation of trialkyltin alkoxide intermediates and allows the preparation of isomeric alkenes from the same precursor by simply changing the reaction temperature.
A Drastic Effect of TEMPO in Zinc-Catalyzed Stannylation of Terminal Alkynes with Hydrostannanes via Dehydrogenation and Oxidative Dehydrogenation
Kai, Yuichi,Oku, Shinya,Sakurai, Kyoko,Tani, Tomohiro,Tsuchimoto, Teruhisa
supporting information, (2019/08/21)
With a system consisting of a catalytic zinc Lewis acid, pyridine, and TEMPO in a nitrile medium, terminal alkynes coupled with HSnBu3, providing alkynylstannanes with structural diversity. The resulting alkynylstannane, without being isolated, could be directly used for Pd- and Cu-catalyzed transformations to deliver internal alkynes and more intricate tin-atom-containing molecules. Mechanistic studies indicated that TEMPOSnBu3 formed in situ from TEMPO and HSnBu3 works to stannylate the terminal alkyne in collaboration with the zinc catalyst, and that both of dehydrogenation and oxidative dehydrogenation processes are uniquely involved in a single reaction. (Figure presented.).
Polyoxometalate-catalyzed insertion of oxygen from O2 into tin-alkyl bonds
Khenkin, Alexander M.,Efremenko, Irena,Martin, Jan M. L.,Neumann, Ronny
supporting information, p. 19304 - 19310 (2014/01/17)
The polyoxometalate H5PV2Mo10O 40 mediates the insertion of an oxygen atom from H5PV 2Mo10O40 into the tin-carbon bond of n-Bu 4Sn through its activation by
Metal-catalyzed reduction of HCONR'2, R' = Me (DMF), et (DEF), by silanes to produce R'2NMe and disiloxanes: A mechanism unraveled
Arias-Ugarte, Renzo,Sharma, Hemant K.,Morris, Andrew L.C.,Pannell, Keith H.
, p. 848 - 851 (2012/03/07)
We demonstrate that using Mo(CO)6, Mo(CO)5NMe 3, and (η5-C5H5)Mn(CO) 3 as catalysts for the silane, R3SiH, reduction of N,N-dimethylformamide (DMF), and N,N-diethylformamide (DEF), we can observe, intercept, and isolate, the important siloxymethylamine intermediates, R 3SiOCH2NR'2, R' = Me, Et, for the first time. In the presence of excess DMF such intermediates thermally react with a variety of silanes to form the corresponding disiloxanes in the absence of a metal catalyst. We also show that the germanium hydrides, Et3GeH and Bu3GeH, also reduce DMF to form trimethylamine and the corresponding digermoxane but observe no intermediates R3GeOCH2NMe 2. Bu3SnH reduces DMF, but along with the low yields of Bu3SnOSnBu3 (but no Bu3SnOCH 2NMe2) significant side products are obtained including (Bu3Sn)2 and Bu4Sn. In the absence of DMF the siloxymethylamines can undergo metal-catalyzed reactions with silanes, germanes and stannanes to form disiloxanes, and R3SiOER3 E = Ge, Sn, respectively. To date, the most efficient catalyst for this latter process is (η5-C5H5)Mo(CO)3CH 3 via a photochemical reaction.
Stereoselective radical tandem cyclohydrostannation of optically active di-unsaturated esters of TADDOL
Gerbino, Dario C.,Koll, Liliana C.,Mandolesi, Sandra D.,Podesta, Julio C.
, p. 660 - 665 (2009/01/30)
This paper reports the results obtained in a study on the radical addition of triorganotin hydrides, R3SnH (R = Me, n-Bu, Ph; Neophyl), to four TADDOL unsaturated diesters. It was found that diese reactions lead in high yields to products of cyclohydrostannation. It was also found that whereas the addition of these hydrides to TADDOL diacrylate and TADDOL dimethacrylate leads to the expected mixtures of two and four cycloundecane diastereoisomers, respectively, the addition of triphenyltin hydride to TADDOL disubstituted acrylates yields only four out of the 16 possible stereoisomers. The observed high stereoselectivity is consistent with the radical tandem cyclohydrostannation mechanism proposed. Only in the case of the hydrostannation of TADDOL diacrylate with trimethyl- and triphenyltin hydrides could the diastereoisomers obtained in higher proportion (5a and 8a) be isolated in pure form. The subsequent reduction (lithium aluminum hydride) of macrolides 5a and 8a afforded the corresponding optically active diols 26 and 27 in high yield. Full 1H, 13C, and 119Sn NMR data are given.
Structural investigations on diorgano- and triorganotin(IV) derivatives of [meso-tetra(4-sulfonatophenyl)porphine] metal chlorides
Pellerito,Scopelliti,Fiore,Nagy,Barone,Abbate,Stocco,Pellerito
, p. 1573 - 1583 (2007/10/03)
Several new complexes of organotin(IV) moieties with MCl n[meso-tetra(4-sulfonatophenyl)porphine], (R2Sn) 2MCln[meso-tetra(4-sulfonatophenyl)-porphinate]s and (R3Sn)4MCln [meso-tetra(4-sulfonatophenyl) porphinate]s, [M = Fe(III), Mn(III): n = 1, R = Me, n-Bu; Ph; M = Sn(IV): n = 2, R = Me, n-Bu] have been synthesized and their solid state configuration investigated by infrared (IR) and M?ssbauer spectroscopy, and by 1H and 13C NMR in D2O. The electron density on the metal ion coordinated inside the porphyrin ring is not influenced by the organotin(IV) moieties bonded to the oxygen atoms of the side chain sulfonatophenyl groups, as it has been inferred on the basis of M?ssbauer spectroscopy and, in particular, from the invariance of the isomer shift of the Fe(III) and Sn(IV) atoms coordinated into the porphyrin square plane of the newly synthesized complexes, with respect to the same atoms in the free ligand. As far as the coordination polyhedra around the peripheral tin atoms are concerned, infrared spectra and experimental M?ssbauer data would suggest octahedral and trigonal bipyramidal environments around tin, in polymeric configurations obtained, respectively, in the diorganotin derivatives through chelating or bridging sulfonate groups coordinating in the square plane, and in triorganotin(IV) complexes through bridging sulfonate oxygen atoms in axial positions. The structures of the (Me3Sn)4Sn(IV)Cl 2[meso-tetra(4-sulfonatophenyl)porphinate] and of the two model systems, Me3Sn(PS)(HPS) and Me2Sn(PS)2 [HPS = phenylsulfonic acid], have been studied by a two layer ONIOM method, using the hybrid DFT B3LYP functional for the higher layer, including the significant tin environment. This approach allowed us to support the structural hypotheses inferred by the IR and M?ssbauer spectroscopy analysis and to obtain detailed geometrical information of the tin environment in the compounds investigated. 1H and 13C NMR data suggested retention of the geometry around the tin(IV) atom in D2O solution.
Reactions of organolanthanide compounds RLnI (Ln = Yb, Eu, Sm) with organic derivatives of silicon, tin, lead, and antimony
Rybakova,Syutkina,Petrov
, p. 244 - 246 (2007/10/03)
Reactions of compounds RLnI (R = Alk, Ar; Ln = Yb, Eu, Sm) with hexaalkyl(aryl)-distannanes, trimethylsilyltriphenyltin, and lead and antimony acetates were studied. The reactions with Sn-Sn and Si-Sn organic derivatives result in cleavage of Sn-Sn amd Sn-Si bonds with formation of tetrasubstituted stannanes and reactive organometallic derivatives with an Sn-Ln or Si-Ln bond. The reactions of RYbI with lead and antimony acetates and with tetraethoxysilane cause cleavage of the Pb-O, Sb-O, or Si-O bond with formation of tetrasubstituted derivatives of lead and silicon or trisubstituted antimony derivatives.
Reactivity of carbon dioxide with n-butyl(phenoxy)-,(alkoxy)-, and (oxo)stannanes: insight into dimethyl carbonate synthesis
Ballivet-Tkatchenko,Douteau,Stutzmann
, p. 4563 - 4567 (2008/10/08)
The CO2 insertion into Sn-O bonds of a series of butyl(phenoxy)-, (alkoxy)-, and (oxo)-stannanes has been investigated. The tributyl derivatives Bu3SnOR (2a, R = Me; 3a, R = iPr; 4a, R = tBu; 5a, R = SnBu3)1 give quantitatively Bu3Sn(OCO2R), 2b-5b; the analogous tributylphenoxystannane, 1, is less reactive. For the dibutyl series, Bu2Sn(OR)2, steric effects of tBu groups in OR (8a) suppress carbonation under atmospheric pressure. With R = Me (6a) or R = iPr (7a), only one Sn-OR bond reacts, resulting in Bu2Sn(OR)(OCO2R), 6b or 7b. Treating 6a with 2-propanol affords under CO2 the mixed compound Bu2Sn(OMe)-(OCO2iPr), selectively. Facile deinsertion of CO2 is a common property of all compounds, occurring more readily in the dibutyl series. The stoichiometric transformation of the carbonato ligand in 2b, 5b, or 6b to dimethyl carbonate (DMC) on reaction with MeI requires nucleophilic assistance by F- to proceed. In the presence of MeOH, 2b and 5b are almost inactive for DMC formation, in contrast with 6b. The best yield is obtained under supercritical CO2-methanol conditions.
Process for the fractional production of alkytin oxide
-
, (2008/06/13)
A process for the fractional production of alkyltin oxides which comprises the steps of: subjecting a mono-, di- or trialkyltin halide to continuous hydrolysis at a temperature between 30° to 100° C. for a period of 10 minutes to 3 hours by the use of a 1% to 50% aqueous solution of a basic substance, thereby forming in the hydrolysis reaction mixture a dialkyltin oxide having an average particle diameter of 10 μm or more, provided that where an intended alkyltin oxide is solid, the continuous hydrolysis is performed in the presence of an organic solvent slightly soluble in water and having a boiling point as measured under ordinary pressure of 150° C. or lower and a specific gravity of 1.1 or smaller; allowing the resulting reaction mixture to stand, thereby to form three phases composed of an organic phase, an aqueous phase, and a phase consisting substantially of the dialkyltin oxide and having a specific gravity 0.02 or more larger than that of the aqueous phase; separating the three phases from one another; and isolating a bis(trialkyltin) oxide or a trialkyltin hydroxide from the organic phase, a monoalkyltin oxide from the aqueous phase, and the dialkyltin oxide from the phase consisting substantially of the dialkyltin oxide and having a specific gravity 0.02 or more larger than that of the aqueous phase.
