有机过渡金属五卤苯基化合物的研究——Ⅲ.(Ph_2PR)_2Co(C_6Cl_5)_2的有效配位数及其在苯溶液中的构型转化

(Ph_2PR)_2Co(C_6Cl_5)_2型化合物(R=Me,Et,n-Pr,n-Bu)中,Co(Ⅱ)的有效配位数可以通过膦上适当位置氢原子的成桥作用变成6.配位可以在固相完成(R=Et,n-Pr),也可以在溶液中完成(R=Me,n-Bu),在溶液中进行的配位过程具有自催化反应的特点.六配位化合物在溶液中慢速地向四配位四面体构型转化(R=Me 的化合物例外),这种转化服从一级过程规律.     

有机过渡金属五卤苯基化合物的研究XI.(Ph2PR)2Co(C6Cl5)2在苯溶液中的构型转化平衡

测定了化合物(Ph2PR)3Co(C5Cl5)2(R=Et,n-Pr)在苯溶液中型转化的热力学和动力学参数,讨论了这种涉及附加配位的新型转化平衡.初始和平衡的八面体构型有不同的附加配位,苯基邻位氢配位比R基端位氢配位更为稳定.四面体构型的稳定性较低,构型转化主要受R基的推动.     

有机过渡金属五卤苯基化合物的研究Ⅺ.(Ph_2PR)_2Co (C_6Cl_5)_2在苯溶液中的构型转化平衡

本文测定了化合物(Ph_2PR)_2Co(C_6Cl_5)_2(R=Et,n-Pr)在苯溶液中构型转化的热力学和动力学参数,讨论了这种涉及附加配位的新型构型转化平衡。初始和平衡的八面体构型有不同的附加配位,苯基邻位氢配位比R基端位氢配位更为稳定,四面体构型的稳定性较低,构型转化主要受R基的推动。     

含硅二烃基锡(Ⅳ)的2-巯基苯并噻唑配合物的合成、结构及抗癌活性

合成了6个含硅二烃基锡(IV)的2-巯基苯并噻唑配合物R1R2Sn L2(R1=Me3Si CH2,R2=Me3Si CH2或Ph,Cy;R1=Et Me2Si CH2,R2=Et Me2Si CH2或Ph,Cy.LH=2-硫基苯并噻唑),并通过IR、1H NMR、13C NMR、元素分析和X射线单晶衍射对目标化合物进行结构表征.结果表明,配体L以硫醇互变异构体形式与锡原子配位,形成了以锡为中心的六配位扭曲八面体结构;生物活性试验的初步结果显示,含硅二烃基锡(IV)-2-巯基苯并噻唑对肺腺癌细胞(A549)具有较强的体外抗癌活性.     

含硅二烃基锡(Ⅳ)水杨醛缩氨基硫脲席夫碱配合物的合成、结构及抗癌活性

合成了11个含硅二烃基锡的水杨醛缩氨基硫脲席夫碱配合物R(Me3SiCH2)SnL(R=Me3SiCH2或Ph,Cy;H2L=水杨醛缩氨基硫脲席夫碱),并通过1H NMR、13C NMR、IR、元素分析和X射线单晶衍射对目标化合物结构进行了表征。结果表明,水杨醛缩氨基硫脲席夫碱作为三齿双阴离子配体,通过酚氧、亚胺氮和硫醇硫与锡(Ⅳ)配位,形成了中心锡原子为五配位的五元杂环与六元杂环的并联结构。生物活性试验的初步结果显示,该类化合物对人体乳腺癌细胞MDA-MB-231和MCF-7具有较好的体外抗癌活性。     

[(η5-C5Me5)WS3Cu3Br2(PPyPh2)2]四核簇合物的合成和晶体结构

以2[(η5-C5Me5)WS3(CuBr)3]2和diphenyl-2-pyridylphosphine (PPyPh2)在乙腈中反应得到标题化合物[(η5-C5Me5)WS3Cu3Br2(PPyPh2)2], 对该产物进行了元素分析、 IR、 UV-Vis和1H NMR 谱表征, 并测定了晶体结构. 该化合物晶体属三斜晶系, P1空间群, 晶胞参数: a=1.545 9(7) nm, b=1.62 0(1) nm, c=1.018 0(2) nm, α=94.18(3)°, β=97.38(3)°, γ=111.81(4)°, V=2.327(2) nm3, Z=2, Dc=1.84 g*cm-3, F(000)=1 260, μ=57.77 cm-1, 最终偏离因子R=0.029. 此簇合物结构可视为由一个[(η5-C5Me5)WS3]单元和3个Cu组成的开口立方烷, 其中2个Cu是畸变四面体配位, 第3个Cu是近似三角平面配位. W-Cu(1), W-Cu(2) 和W-Cu(3)距离分别为0.270 41(9), 0.273 27(8), 0.267 85(9) nm.     

配合物Nd(C7H7N2O2)3(H2O)3的合成及其晶体结构

用水热法合成了3,5-二氨基苯甲酸与Nd(Ⅲ)的配合物Nd(C7H7N2O2)3(H2O)3(1),其结构经IR,元素分析和X-射线单晶衍射仪表征。1为单核结构,属六方晶系,R3空间群,晶胞参数:a=1.887 29(18)nm,b=1.887 29(18)nm,c=0.603 53(12)nm,β=90,°γ=120°,V=1.861 7(4)nm3,Z=3,μ=2.154 mm-1,Dc=1.744 g.cm-3,R1=0.014 3,wR2=0.033 2。1中Nd(Ⅲ)与来自3个3,5-二氨基苯甲酸的6个氧原子及3个配位水的氧原子进行配位,形成9配位化合物。     

[Ni(C_5H_5N)_2(C_7·H_6O_2N)_2]H_2O三元配合物的合成及晶体结构

合成了标题化合物。该化合物的分子式[Ni(C5H5N)2(C7H6O2N)2]H2O(C24H24N4NiO3),分子量475.18,采用单色的MoKα (λ = 0.71073 )射线测定,共收集7408个数据,其中独立衍射点2567个(Rint = 0.0272),I > 2s(I)可观测点数1926个,结果表明该化合物属单斜晶系, 空间群C2/c其晶胞参数为: a = 14.466(2),b = 12.193(2),c = 14.072(2) ;β = 116.229(2)°,V = 2226.6(5) 3,Z = 4,Dc = 1.418 g/cm3 ,μ = 0.905 mm-1,F(000) = 992. 2个水杨醛亚胺各提供2个配位原子参与配位,2个吡啶各提供1个配位原子参与配位,该配合物是六配位的八面体构型,同时讨论了该体系中不同配位原子的配位能力的差异。     

氧桥联双核铁(Ⅲ)配合物[Fe2(μ-O)(TPA)2Cl2](ClO4)2的合成和晶体结构

标题化合物是FeCl3·6H2O和TPA·3HClO4(TPA=(C6H6N)3N) 在甲醇溶液中反应得到的橙色晶体.X-射线衍射测定了其单晶结构.结果表明,该晶体属单斜晶系,C2/c空间群.化学式:C36H36Cl4Fe2N8O9, Mr=978.22, a=16.300(3), b=17.180 (3)(S), c=16.582(3), β=111.75(3)°, V=4131(S)3, Z=4, Dc=1.299 g/cm3, μ(MoKα) = 8.43 cm-1, 4211个可观测衍射点,R=0.043, RW=0.049.分子中氧原子桥联两个铁(Ⅲ) 原子, TPA上的4个氮原子和1个氯离子分别占据铁(Ⅲ)原子的其余5个配位位置, 形成6配位畸变8面体构型.     

含R_2dtc配体Mo-Cu化合物的动态~(95)Mo NMR

本实验利用动态~(95)Mo NMR监测Mo-Cu系列化合物的形成过程,对反应CuCl+NaR_2dtc+MoO_nS,摩尔比3:3:1,溶剂为DMF;R=Et,n=0(Ⅰ);R=Me,n=0(Ⅱ);R=Et,n=2(Ⅲ)进行了研究,观察到具有不同簇骼的多种中间产物的存在及随反应进程相互转化等现象。     

Alcoholysis of (2-methoxycarbonyl)ethyltin compounds

Under acid or base catalysis, di(2-alkoxycarbonylethyl)tin dichlorides of various R groups, (ROCOCH₂CH₂)₂SnCl₂, can be prepared conveniently in high yield by alcoholysis of (CH₃OCOCH₂CH₂)₂SnCl₂ in various alcohols, ROH (R = C₂H₅, C₄H₉, iso-C₄H₉, C₅H₁₁, C₆H₅CH₂, C₄H₉CH(C₂H₅)CH₂). When excess acid or base is present in the aqueous solution, (ROCOCH₂CH₂)₂SnCl₂ eliminate ROH and precipitate as C₆H₈O₄Sn regardless of the R group. C₆H₈O₄Sn can be converted into various (ROCOCH₂CH₂)₂SnCl₂ derivatives on dissolving in alcoholic HCl solutions.     

Preparation of trimethyl-2-hydroxyethylarsonium (arsenocholine) compounds

Trimethyl-2-X-ethylarsonium salts (X=OH, Cl, Br, CH₃COO; anion=Br) and trimethyl-2-diethoxyethylarsonium bromide were prepared from trimethylarsine and the appropriate organic bromides in sealed tubes at elevated temperatures or by refluxing the neat reagents. The yields ranged from 33 to 85%. Anion exchange reactions produced the arsonium iodides, nitrates, acetates, tosylates, tetraphenylborates, picrates, hydroxides, and carbonates. Arsenocholine bromide (X=OH) was phosphorylated with concentrated phosphoric acid. The product was isolated as the barium salt. Treatment of the barium salt with sulfuric acid yielded trimethyl-2-(dihydrogen phosphato)ethylarsonium bromide. These substances were synthesized to serve as precursors for arsenic- containing phospholipids and as standards for the chromatographic identification of arsenocholines. The synthesized compounds were characterized by elemental analyses and ¹H and ¹³C NMR spectroscopy. The shifts of the arsenic compounds were compared with those of the corresponding nitrogen compounds and found to be sufficiently different to be used for the identification of these compounds in their mixtures.     

Synthesis of 2-(2-methoxyethyl)- and 2-(2-thiomethoxyethyl)-aniline and related compounds

Summary 2-(2-Nitrophenyl)-ethanol (2) was methylated with dimethyl sulfate to give 2-(2-methoxyethyl)-1-nitrobenzene (3a) which then was reduced with hydrazine hydrate in the presence ofRaney nickel to 2-(2-methoxyethyl)-aniline (1a). Compound1a can be transformed into the N-monosilylated derivative4 by lithiation withn-butyllithium and subsequent reaction with chlorotrimethylsilane. Reaction of2 withp-toluenesulfonyl chloride yields 2-(2-nitrophenyl)-ethylp-toluenesulfonate (5), which reacts with sodium thiomethoxide to give 2-(2-nitrophenyl)-ethylp-toluenesulfonate (5), which reacts with sodium thiomethoxide to give 2-(2-thiomethoxyethyl)-1-nitrobenzene (3b).3b was reduced with hydrazine hydrate in the presence ofRaney nickel to yield 2-(2-thiomethoxyethyl)-aniline (1b). Ethyl (2-nitrophenyl)-acetate (6) could be dimethylated with methyl iodide in the presence of potassiumtert-butoxide and 18-crown-6 to give ethyl 2-methyl-2-(2-nitrophenyl)-propionate (7). Reduction of7 with lithium borohydride yields 2,3-dihydro-3,3-dimethyl-1H-indole (9) and 2-[(1-hydroxy-2-methyl)-2-propyl]-aniline (10).

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Synthese von 2-(2-Methoxyethyl)- und 2-(2-Thiomethoxyethyl)-anilin und verwandten Verbindungen

Zusammenfassung 2-(2-Nitrophenyl)-ethanol (2) wurde mit Dimethylsulfat zu 2-(2-Methoxyethyl)-1-nitrobenzol (3a) methyliert, das sich mit Hydrazinhydrat in Gegenwart vonRaney-Nickel zu 2-(2-Methoxyethyl)-anilin (1a) reduzieren läßt. Verbindung1a kann durch Metallierung mitn-Butyllithium und anschließende Reaktion mit Chlortrimethylsilan in dasN-monosilylierte Derivat4 umgewandelt werden. Reaktion von2 mitp-Toluolsulfonylchlorid ergab 2-(2-Nitrophenyl)-ethyl-p-Toluolsulfonat (5), das mit Natriumthiomethanolat zu 1-Nitro-2-(2-thiomethoxyethyl)-benzol (3b) reagiert.3b wurde mit Hydrazinhydrat in Gegenwart vonRaney-Nickel zu 2-(2-Thiomethoxyethyl)-anilin (1b) reduziert. Ethyl-2-(nitrophenyl)-acetat (6) kann mit Methyliodid in Gegenwart von Kalium-tert-butoxid und 18-Krone-6 zu Ethyl-2-methyl-2-(2-nitrophenyl)-propionat (7) dimethyliert werden. Reduktion von7 mit Lithiumborhydrid lieferte 2,3-Dihydro-3,3-dimethyl-1H-indol (9) und 2-[(1-Hydroxy-2-methyl)-2-propyl]-anilin (10).

     

The synthesis of 2-(2-furyl) 1,3-dicarbonyl compounds

2-furyl derivatives are easily synthesised by intermolecular condensation of 2,5-dihydro-2,5-dimethoxy furan (DHDMF) with active methylene compounds by a simple and cheap procedure. The reaction applies only to 1,3-dicarbonyl compounds and a general mechanism is proposed.     

E2(CN)2 (E = S, Se) and related compounds

A synthetic, spectroscopic, and theoretical study of Ex(CN)2 (E = S, Se; x = 1-3) is described. The X-ray structures of Se2(CN)2 and Se3(CN)2 have been determined. Se2(CN)2 crystallizes in a chiral space group with the CN groups approximately gauche.     

Thallophilic interactions in aryloxide compounds: the [Tl2(mu2-OAr)4] structural motif in (TlOAr)4 and Tl2Cu(OAr)4 compounds

Two thallium aryloxide compounds TlOC6F5 (TlOAr(F)) and bis-3,5-TlOC6H3(CF3)2 (TlOAr') have been recrystallized from THF and crystallographically characterized in different isomeric forms. The latter compound forms a solvated tetrameric cubane, [TlOAr']4.THF, 1. The TlOAr(F) compound crystallized with a similar stoichiometry, [TlOAr(F)]4.2 THF, 2, but contains a [Tl2(mu2-OAr(F))4] unit that includes a thallophilic interaction at a distance of 3.5943(15) angstroms. Solution 205Tl and 203Tl NMR studies of 1 and 2 support the retention of a cubane structure for 1 in solution and suggest a similar structure for 2 with coupled thallium centers down to -90 degrees C. Fluorescence spectroscopy data for both compounds 1 and 2 in THF are consistent with LMCT. DFT calculations of 1, 2, and three models of the [Tl2(mu2-OAr(F))4] unit show a bonding overlap of the bridged thallium atoms in 2 and are also used to describe the bonding in 1. The structures of two heterobimetallic compounds, Tl2Cu(OAr(F))4, 4, and Tl2Cu(OAr')4, 5, with the [Tl2(mu2-OAr(F))4] structural motif and thallophilic contacts of 3.86(6) and 3.564(1) angstroms, respectively, are described. The crystal structures of the unsolvated of TlOAr(F), 2b, solvated heterobimetallic derivative Tl2Cu(OAr')4.2THF, 5b, and the monomeric (18-crown-6)TlOAr(F), 3, and 205Tl NMR spectra of TlOC6H5, 6, are also reported for comparison purposes.     

Additional NMR data on compounds of the type cis-Ti(AA)2X2

Previous work has shown that $\text{cis}$-disubstituted (acac)₂ titanium (IV) complexes exist in solution as nonrigid molecules [1]. These studies were followed by variable temperature ¹H NMR spectroscopy. The spectra shows that for the dialkoxy and dihalo complexes the acetylacetonate (acac) rings exchange the methyl groups between the two nonequivalent sites of the cis isomer. These rearrangements take place $\text{via}$ an intramolecular rearrangement: both twisting and one bond rupture mechanisms have been suggested for these stero-chemical rearrangements [2-4].