含锆(Ⅳ)、锡(Ⅳ)、钛(Ⅳ)的酰腙及硫代酰腙配合物的合成与表征

选用二氯二茂锆、二氯二苯基锡、四氯化锡和四氯化钛为底物,以酰腙、硫代酰腙为配体合成了9个含钛、锆、锡的单核或双核金属有机配合物并对其结构进行了元素分析和IR、NMR分析,其中α-羟基苯甲醛丙二酰腙与二氯二苯基锡缩合生成的双核金属配合物首次获得单晶并由X射线衍射分析确认了其结构。     

Biphenolate phosphine complexes of tin(IV)

The preparation and structural characterization of tin(IV) complexes supported by (2,2'-phenylphosphino)bis(4,6-di-tert-butylphenolate) ([OPO]2-) are described. The reaction of in-situ prepared Li2[OPO] with SnCl4 in THF at -35 degrees C produced [OPO]SnCl2(THF) as a THF adduct. Addition of SnCl4 to a THF solution of H2[OPO] in the presence of 2 equiv of NEt3 at room temperature led to the formation of the "ate" complex {[OPO]SnCl3}(HNEt3). The metathetical reactions of Li2[OPO] with R2SnCl2 (R=Me, n-Bu) in THF at -35 degrees C generated the corresponding five-coordinate dialkyl complexes [OPO]SnR2. In addition to the multinuclear NMR spectroscopic data for all new compounds, X-ray structures of [OPO]SnCl2(THF), [OPO]SnMe2, and [OPO]Sn(n-Bu)2 are presented.     

SnCl4催化丙酮与过氧化氢反应制取大环过氧化物

H₂O₂与过渡金属构成的催化体系可选择性地氧化烃类化合物,如芳烃的羟基化和烯烃的环氧化等^[1～3],且H₂O₂在应用中无环境污染,是一种颇有前途的氧化剂.有关金属催化H₂O₂与酮类化合物反应的报道很少.     

The dimerization of SnCl2(g): mass spectrometric and theoretical studies

The vaporization of SnCl2(s) was investigated in the temperature range between 382 and 504 K by the use of Knudsen effusion mass spectrometry. The Sn+, SnCl+, SnCl2+, Sn2Cl3+, and Sn2Cl4+ ions were detected in the mass spectrum of the equilibrium vapor. The SnCl2(g) and Sn2Cl4(g) gaseous species were identified, and their partial pressures were determined. The structure and vibrational properties of both species and corresponding fragmentation products were studied applying density functional theory and second-order M?ller-Plesset perturbation theoretical approaches. Molecular parameters yielded thermodynamic functions by the use of statistical thermodynamics. The sublimation enthalpies of SnCl2(g) and Sn2Cl4(g) at 298 K resulting from the second- and third-law methods are evaluated as 130.9 +/- 6.2 kJ mol(-1) and 155.8 +/- 7.3 kJ mol(-1), respectively. The enthalpy changes of the dissociation reactions Sn2Cl4(g) = 2 SnCl2(g) were obtained as delta(d)H degrees(298) = 106.8 +/- 6.2 kJ mol(-1). The corresponding theoretical value amounts to 103.4 kJ mol(-1). The change of monomer properties due to the dimerization reaction is also discussed.     

Capture of phosphorus(I) and arsenic(I) moieties by a 1,2-bis(arylimino)acenaphthene (aryl-BIAN) ligand. A case of intramolecular charge transfer

The reaction of PCl3 with SnCl2 in THF solution, followed by treatment with dpp-BIAN (dpp = 2,6-i-Pr2C6H3), affords the phosphenium complex [(dpp-BIAN)P][SnCl5.THF]. The 31P chemical shift (delta 232.5) and the metrical parameters from a single-crystal X-ray diffraction study indicate that the oxidation state of phosphorus in this compound is +3. A similar conclusion was reached regarding the phosphorus oxidation state in [(dpp-BIAN)P][I3], which was prepared via the reaction of dpp-BIAN with PI3 in CH2Cl2 solution. The arsenium salt [(dpp-BIAN)As][SnCl5.THF] was prepared by treatment of AsCl3 with SnCl2 in THF solution, followed by the addition of dpp-BIAN. The X-ray crystal structure of this salt was determined, and the pattern of bond distances and angles indicates that arsenic is present in the +3 oxidation state.     

微波等离子体光谱法测定碲的研究

微波等离子体原子发射光谱法(MIPAES)测定碲,前人已作过一些工作。本文利用我们建立的微量进样系统与MIPAES联用,对碲的测定进行了研究。实验中发现,加入适量的SnCl_2可降低检出限约一个数量级,Te_(214.3nm)的检出限为5 ng/mL,同时还研究了碱金属卤化物对碲的测定的影响。     

Synthesis,characterization and biological activities of organotin(IV) complexes with l-lysine monohydrate

Russian Journal of General Chemistry - The new organotin(IV) complexes have been synthesized by the reaction of l-lysine monohydrate with CS2 and R2SnCl2/R3SnCl. The organotin(IV) complexes and the...     

Complex Salts Derived from the Reactions of Organotin(IV) with 6-Methylpyridine-2-Carboxaldehyde Phenylhydrazone: X-Ray Crystal Structure of BIS[6-Methylpyridine- 2-Carboxaldehydehydrazodium]- Tetrachlorodimethylstannate(IV)

Reactions of organotin(IV) chloride (Me 2 SnCl 2 , PhSnCl 3 and n -BuSnCl 3 ) with the Schiff base 6-methylpyridine-2-carboxaldehyde phenylhydrazone ( L ) result in the formation of organotin(IV) anionic complexes. Me 2 SnCl 2 reacts with L in dichloromethane to form [ L H + ] 2 [Me 2 SnCl 4 ] 2 m . X-ray structural analysis has been carried out on the complex salt bis[6-methylpyridine-2-carboxaldehydehydrazodium]tetra-chlorodimethylstannate(IV), [ L H + ] 2 [Me 2 SnCl 4 ] 2 m wherein the tin moieties exist as monomers. Reactions of PhSnC1 3 and n -BuSnCl 3 with L form the complexes [ L H + ] 2 [PhSnCl 5 ] 2 m and [ L H + ] 2 [ n- BuSnCl 5 ] 2 m . Compounds were also characterized by FTIR, 1 H and 13 C NMR spectroscopy.     

Cooperative Friedel-Crafts catalysis in heterobimetallic regime: alkylation of aromatics by pi-activated alcohols

The highly active Friedel-Crafts alkylation (FCA) catalyst, [Ir(COD)Cl(SnCl3)(SnCl4)(arene)]+Cl- (1-SnCl4), is easily generated in one-pot from [Ir(COD)Cl]2 or [Ir(COD)(mu-Cl)Cl(SnCl3)]2 (1) and SnCl4. The reaction of arenes, heteroarenes with benzyl, and allyl alcohols is promoted by 1-SnCl4 (1 mol %) with high turnover frequency. Kinetic evidence is presented to establish FCA pattern. From dual-catalyst combination studies varying the transition metal and main group metal partner, the efficiency of the present catalysts is attributed to the electrophilic "IrIII-SnIV" core.     

Metal assembly in novel dendrimers with porphyrin cores

A series of phenylazozmethine (DPA) dendrimers with a porphyrin core (PnH2) were synthesized by dehydration using TiCl4 from meso-tetrakis(4-aminophenyl)porphyrin and the DPA dendrons. The addition of SnCl2 to a dichloromethane/acetonitrile solution of dendritic cobalt porphyrin resulted in a stepwise spectral change. By using UV-vis spectroscopy to monitor the complexation of the P4CoIIICl until an equimolar amount of SnCl2 has been added, four changes in the position of the isosbestic point were observed during the addition of SnCl2. Titration results suggest that four different complexes are successively formed upon the SnCl2 addition and that the complexation proceeds in, not a random, but a stepwise fashion from the core imines to the terminal imines of P4CoIIICl. The electrochemical study reveals that their dendrimers with Tb ion act as a multielectron mediator in CO2 reduction at high applied potential on the electrode.     

Synthesis and characterization of aluminum-containing tin(IV) heterobimetallic sulfides

Three novel aluminum-containing tin(IV) heterobimetallic sulfides are reported. The reaction of [LAl(SLi)2(THF)2]2 (1) [L = HC(CMeNAr)2, Ar = 2,6-iPr2C6H3] with Ph2SnCl2, Me2SnCl2, and SnCl4 in THF respectively afforded LAl(mu-S)2SnPh2 (2), LAl(mu-S)2SnMe2 (3), and LAl(mu-S)2Sn(mu-S)2AlL (4) in moderate yields. Compounds 2, 3, and 4 were characterized by elemental analysis, NMR, electron-impact mass spectrometry, and single-crystal X-ray structural analysis.     

微波促进活性炭负载四氯化锡催化合成乙酰乙酸乙酯缩酮

在微波辐射下,以活性炭负载四氯化锡(SnCl4·5H2O/C)为催化剂,不用溶剂,合成了乙酰乙酸乙酯乙二醇缩酮和乙酰乙酸乙酯1,2-丙二醇缩酮。以乙酰乙酸乙酯与乙二醇缩合为模型反应进行优化,其优化条件是:负载量为20%的SnCl4·5H2O/C催化剂0.1 g,乙酰乙酸乙酯5 mL,乙二醇6 mL,微波辐射功率600 W,辐射时间2.5 min,产率达81.6%。产物经过红外光谱表征。     

Study on the interactions between anti-tumor metal complexes and mononucleotides using trans-[en2Os(η2-H2)(CF3SO3)](CF3SO3) as a 1H NMR probe in a competitive mode

The interaction of several anti-tumor metal complexes with dGMP have been investigated using trans-[en2Os(η2-H2)]2+ as a 1H NMR probe in a competitive mode. Me2SnCl2, Bu2SnCl2, Et2Sn(phen)Cl2 and Et2SnCl2 can bind to dGMP mainly via phosphate; Cp2TiCl2 binds to dGMP mainly via phosphate and N7. The binding constant for (CH3)2SnCl2 binding to phosphate of dGMP exceeds 2.71×104. The binding constant for Cp2TiCl2 to phosphate is even greater than that of Sn(IV). Cis-platin has high affinity for both N7 and phosphate, but mainly for N7. Binding of the probe to N7 of dGMP reduces the binding affinity for phosphate of the same dGMP molecule by a factor of 5 to 6. Much the same factor is expected to apply to other metals containing agents interacting with dGMP.     

Synthesis of SnO_2 nanorods from aqueous solution:The effect of preparation conditions on the formed patterns

<正>SnO_2 nanorods were deposited on the Si substrates in an aqueous solution containing both SnCl_4 and CO(NH_2)_2.It is found that different self-assembled patterns of SnO_2 nanorods can be obtained by changing the deposition conditions such as the molar ratio of CO(NH_2)_2 to SnCl_4 and the pretreatment of the substrate.Scattered SnO_2 nanorods,for example,can be changed into flower-like patterns when the molar ratio of CO(NH_2)_2 to SnCl_4 is raised,and well-aligned nanorod arrays can be formed when the pretreatment of the substrate is changed.In addition,some interesting patterns,e.g.tree-like patterns,can also be observed.     

Catalytic enantioselective allyl- and crotylboration of aldehydes using chiral diol x SnCl4 complexes. optimization, substrate scope and mechanistic investigations

We report a novel class of C2-symmetric chiral diols derived from the hydrobenzoin skeleton. The combination of these diols with SnCl4 under Yamamoto's concept of Lewis acid assisted Br?nsted acidity (LBA catalysis) leads to high levels of asymmetric induction in the allylboration of aldehydes by commercially available allylboronic acid pinacol ester 1a. The corresponding homoallylic alcohol products of synthetically useful aliphatic aldehydes are obtained in excellent yields with up to 98:2 er. This combined acid manifold is also efficient in catalyzing the diastereo- and enantioselective crotylboration of aldehydes, thus providing the propionate units in >95:5 dr and up to 98:2 er. The X-ray crystal structure of the optimal diol x SnCl4 complex, Vivol (4m) x SnCl4, unambiguously shows the Br?nsted acidic character of this LBA catalyst and its highly dissymmetrical environment. Further controls have ruled out a possible boron trans-esterification mechanism with the chiral diol and point to LBA catalyst-derived activation of the pinacol allylic boronates 1. Due to slow dissociation of the diol x SnCl4 complex, a small excess of diol is required in order to suppress a competing racemic cycle catalyzed by free SnCl4.     

氯化亚锡还原法合成4′-氨基黄体酮类苯亚甲基衍生物

以黄体酮为原料,合成了4′-硝基苯亚甲基衍生物3,将其在SnCl2·2H2O/HCl体系中还原后得4′-氨基苯亚甲基衍生物4。 还原时以乙酸乙酯为溶剂,还原剂SnCl2为底物5倍化学计量时产率达74%,为甾类氨基衍生物的合成提供了一种便利方法。     

Ab initio study of low-lying electronic states of SnCl2+

Complete active space self-consistent field (CASSCF), multireference configuration interaction (MRCI), and restricted-spin coupled-cluster singles-doubles with perturbative triples [RCCSD(T)] calculations have been carried out on low-lying doublet and quartet states of SnCl2+, employing basis sets of up to aug-cc-pV5Z quality. Effects of core correlation and off-diagonal spin-orbit interaction on computed vertical ionization energies were investigated. The best theoretical estimate of the adiabatic ionization energy (including zero-point vibrational energy correction) to the X2A1 state of SnCl2+ is 10.093+/-0.010 eV. The first photoelectron band of SnCl2 has also been simulated by employing RCCSD(T)/aug-cc-pV5Z potential energy functions and including Duschinsky rotation and anharmonicity.     

β-烷氧羰基乙基三氯化锡配合物的合成、结构表征及酯交换反应

合成了13个标题化合物ROCOCH2CH2SnCl3.L (R=C1-5烷基;L=DBSO, HMPA), 通过元素分析、IR和1H NMR进行了表征。n-PrOCOCH2CH2SnCl3.DBSO的晶体结构分析表明, 该晶体属正交晶系; 空间群P212121; a=1.062, b=1.427, c=1.635; Z=4。该化合物为含有分子内羰基配位和Lewis碱配位的具有畸变八面体构型的单分子有机锡化合物。研究了CH3OCOCH2CH2SnCl3.L和醇的酯交换反应, 提出了分子内Lewis酸催化的反应机理。     

二氯二乙基锡与DNA作用的研究

利用循环伏安、紫外光谱和粘度测定等手段,对二氯二乙基锡[Et₂SnCl₂]与DNA的作用机制进行了研究.结果明,Et₂SnCl₂主要作用于DNA的骨架磷酸基团,使DNA构象收缩,相对粘度增加,产生减色效应,始终未观察到增色效应.提出了Et₂SnCl₂对DNA可能的作用机制模型.     

Spectrophotometric studies on complex formation in dilute benzene solutions of [{Rh(diene)(μ–Cl)}2]–PR3–SnCl2 systems

There is no correlation between the stability of complexes formed in dilute solutions of [{Rh(diene)(–Cl)}2]–PR3–SnCl2 systems [with ligand combinations cod+PPh3, nbd+PPh3, cod+PPhMe2 and cod+ PCy3 (Cy=cyclohexyl)] and the possibility of isolating them as solids. In general, high dilution favours the formation of pentacoordinate complexes that decompose upon attempted crystallization. [RhCl(cod)(PPhMe2)2], [Rh(SnCl3)(cod)(PPh3)2], [Rh(SnCl3)(cod)(PCy3)2], [Rh(SnCl3)(cod)(PPhMe2)2] and [Rh(SnCl3)(nbd)(PPh3)2] have been identified in solution, but only the last two, previously known, have been isolated in the solid state. The steric properties of the coordinated phosphine seem to be the most important factor in determining the stabilities of [RhCl(diene)(PR3)2] complexes, whilst in the case of [Rh(SnCl3)(diene)(PR3)2] complexes the steric properties of the phosphine and the diene appear to have similar importance.