A General Route to Alkylene-, Arylene-, or Benzylene-Bridged Ditin Hexachlorides and Hexaalkynides
摘要:
The preparation of alkylene-, arylene-, or benzylene-bridged ditin hexachlorides in high yields from the reaction of the corresponding hexacyclohexylated compounds with tin tetrachloride is described. The tetragonal geometry of the tin atom of 1,4-bis(trichlorostannyl)-butane in the solid state indicates that no intramolecular or intermolecular interaction involving either end of the molecule exists in this compound. The ditin hexachlorides were successfully transformed in the corresponding hexaalkynides, precursors of hybrid materials.
α,ω-Bis(trichlorostannyl)alkanes: Unravelling the Hydrolysis Pathway to Organotin-oxo Oligomers
摘要:
New alpha,omega -bis(trichlorostannyl)alkanes, Cl3Sn(CH2)(n)SnCl3 [n = 3-5, 8], have been synthesized via tin-phenyl bond cleavage reactions on alpha,omega -bis(triphenylstannyl)alkanes, Ph3Sn(CH2)(n)SnPh3 [n = 3-5, 8], using either SnCl4 or concentrated hydrochloric acid. Some key missing links, (H2O)Cl3Sn(CH2)(3)SnCl3(H2O) (1a) and (H2O)(2)Cl3Sn(CH2)(3)SnCl3(H2O)(2) (6), in the hydrolysis pathway of organotin trichlorides were identified. Crystal structures of the nonassociated di-tin compounds (H2O)Cl3Sn(CH2)(3)SnCl3(H2O) (1a) and (H2O)(2)Cl3Sn(CH2)(3)SnCl3(H2O)(2) (6, isolated as the 18-crown-6 cocrystal acetonitrile solvate) as well as the polymeric hydrolysis product [H2O(OH)Cl2Sn(CH2)(3)SnCl2(OH)H2O . 2H(2)O](n) (7 . 2H(2)O) are reported.
Preparation and Conformation of Organo-Bridged Bis[tris(arylchalcogenolato)tin] Compounds - An Experimental and Quantum Chemical Study
作者:Hari Pada Nayek、Heiko Niedermeyer、Stefanie Dehnen
DOI:10.1002/zaac.200800263
日期:2008.12
Seven organo-bridged bis[tris(arylchalcogenolato)tin] compounds with the general formulae (R′E)3Sn–R–Sn(ER′)3 (R = –(CH2)4–, 1,4-bis(methyl)benzene, 4,4′-bis(methyl)biphenyl; R′ = Ph, 1-Np, 2-Np; E = S, Se) were synthesized and characterized by means of X-ray diffractometry as well as NMR spectroscopy. Three different conformations of the arylchalcogenolato groups ER′ with respect to the bridging group
具有通式 (R'E)3Sn–R–Sn(ER')3 (R = –(CH2)4–, 1,4-bis(methyl)) 的七种有机桥连双[三(芳基硫属元素)锡]化合物苯,4,4'-双(甲基)联苯;R' = Ph, 1-Np, 2-Np; E = S, Se) 合成并通过 X 射线衍射和核磁共振光谱表征。通过量子化学研究合理化和解释了芳基硫属化合物基团 ER' 相对于桥接基团 R 的三种不同构象。
Synthesis and structural characterization of new organotin derivatives of polyoxotungstates via transmetallation and coupling reactions
作者:Nebebech Belai、Michael T. Pope
DOI:10.1016/j.poly.2006.01.012
日期:2006.6
Organotin-substituted polyoxometalates [WM(RSn)(2)(MW9O34)(2)](10-): (M = Co, Zn: R = CH3. C2H5, n-C4H9) have been prepared through exchange reaction of [WM3(H2O)(2)(MW9O34)(2)](12-) and the appropriate organotin trichloride in aqueous solution. The complexes have been characterized in solution by W-183 and Sn-119 NMR spectroscopy of the diamagnetic anions, and by single crystal structure determinations of salts of the methyl, ethyl and n-butyl derivatives of the tungstozincates and of the methyl derivative of a CoZn2 analog. Cyclic voltammetry demonstrates for the first time for this class of polyoxometalates that the tetrahedral cobalt(II) centers are reversibly oxidizable to yield high-spin cobalt(III) analogs. Displacement of the kinetically metastable [W5O18](6-) anion from [Ce(W5O18)(2)](10), by reaction with CH3SnCl3, leads to modest yields of [CH3SnW5O18](3-) Bis(trictilorostannyl)alkanes such as Cl3Sn(CH4SnCl3 can be used as covalent linkers of polyoxometalate anions to form the "dumbbell" complex [SiW11O39)Sn(CH2)(4)SnSiW11O39](10-) and linear oligomers [(Sn(CH)(40)Sn)(WZn(ZnW9O34)(2))](10-)}(x). (c) 2006 Elsevier Ltd. All rights reserved.
α,ω-Bis(trichlorostannyl)alkanes as Bis(monodentate) Lewis Acids toward Halide Ions
作者:Bernhard Zobel、Andrew Duthie、Dainis Dakternieks、Edward R. T. Tiekink
DOI:10.1021/om010246s
日期:2001.7.1
The reactions between X3Sn(CH2)(n)SnX3 (X = Cl, Br; n = 1, 3, 4, 8) and halide in solution are described. Sn-119 NMR spectroscopy (CD2Cl2) indicates formation of five-coordinate dinuclear 1:2 adducts, [X4Sn(CH2)(n)SnX4](2-), with chloride and bromide. A trigonal-bipyramidal geometry has been confirmed in, the solid state for the compound having X = CI and n = 4. In contrast, fluoride reacts with X3Sn(CH2)(n)SnX3 to give six-coordinate tin species, [F5Sn(CH2)(n)SnF5].(4-) There was no evidence indicating that the tin atoms could act as a bidentate acid.
A Heterometallic, Heterovalent Cu<sup>I</sup>/Sn<sup>II/IV</sup>/S Cluster with an Unprecedented Cu<sub>4</sub>Sn Core and Stannacyclopentane Units
作者:Hari Pada Nayek、Werner Massa、Stefanie Dehnen
DOI:10.1021/ic8013877
日期:2008.10.20
[(Ph3PCuI)(6)(CH2)(4)(SnS2)-S-IV}6Cu(4)(I)Sn(II)], a walnut-type, heterometallic, heterovalent cluster, as confirmed by density functional theory calculations, was obtained under reductive solvothermal conditions and features an unprecedented metalloid core within a metal sulfide shell and an organic surface.