Synthesis and Structure of Tetrahydrofuran Adduct of Tris(indenyl)dysprosium

１　ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｉｎｖｅｓｔｉｇａｔｉｏｎｏｆｔｈｅｓｔｒｕｃｔｕｒｅｓｏｆｏｒｇａｎｏｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｈａｓｂｅｅｎｏｆｉｎｔｅｒｅｓｔｆｏｒｍａｎｙｙｅａｒｓｂｅｃａｕｓｅｉｔｉｓｉｍｐｏｒｔａｎｔｔｏｉｎｔｅｒｐｒｅｔｔｈｅｂｏｎｄｎａｔｕｒｅａｎｄｃｈｅｍｉｃａｌｐｒｏｐｅｒｔｉｅｓｏｆｔｈｅｓｅｃｏｍｐｌｅｘｅｓ〔１〕．Ｃｒｙｓｔａｌｓｔｒｕｃｔｕｒｅｓｏｆｔｒｉｓ（ｉｎｄｅｎｙｌ）ｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓ,ｓｕｃｈａｓ（Ｃ９Ｈ…     

UV-Vis Spectroscopy,Electrochemical and DFT Study of Tris(β-diketonato)iron(III) Complexes with Application in DSSC: Role of Aromatic Thienyl Groups

A series of tris(β-diketonato)iron(III) complexes, with the β-diketonato ligand bearing different substituent groups, have been synthesized and characterized by Fourier transform infrared (FT-IR), ultraviolet-visible (UV-Vis) and mass spectroscopic methods. The maximum band UV-Vis absorption wavelengths of the tris(β-diketonato)iron(III) complexes were in the range of 270–380 nm. The complexes have very good solubility in various solvents such as chloroform, dichloromethane, ethyl acetate, tetrahydrofurane, dimethylsulphoxide and dimethylformamide. After the syntheses and characterization processes, spectroscopic and electrochemical properties of these tris(β-diketonato)iron(III) complexes were investigated. A density functional theory (DFT) study related to the spectroscopic and electrochemical properties of the tris(β-diketonato)iron(III) complexes was used to investigate the possible application of these complexes as dye sensitizers or redox mediators in dye-sensitized solar cells.     

Base-catalyzed Formation of Enamines from β,β-Dicyanostyrene Derivatives with N-Bromosaccharin

A new method for the synthesis of functional enamines from β,β-dicyanostyrene derivatives and N-bromosaccharin(NBSA) was developed. In the presence of Na₂CO₃, the the reaction of β,β-dicyanostyrene derivatives with NBSA can generate the corresponding enamines smoothly in a mixed solvent of dichloromethane and N,N-dimethylformamide (DMF)(volume ratio 1:1) at 50℃. The reaction of 14 kinds of β,β-dicyanostyrene derivatives with NBSA was investigated. Screened olefins afforded the corresponding enamines in good to excellent yields(up to 94%), indicating that the method has a wide adaptability for the substrate. The catalyst used is inexpensive and stable for storage. The amino groups of all products in their structures are on the α-position of products, revealing the reaction has an excellent regioselectivity. The possible pathway involving aminobromination of β,β-dicyanostyrene derivative with NBSA first and then elimination of HBr process in one pot has been proposed. The structures of all products were confirmed by ¹H NMR, ¹³C NMR and HRMS analysis.     

β-萘甲酰化β-环糊精的分子识别性能研究

最近二十年,外形似“锥简”,腔内疏水,脏外亲水的环糊精（Cyclodextrin,CD包括a,o,7－CD等）,以其特有的结构在模拟酶、分子识别等众多领域内深受广大科学工作者重视［’－‘］．为了获得更有效的模拟酶及分子识别功能体,我们已合成并报道了一系列含有发色基团的CD衍生物卜一句．本文利用基紫外光谱对产一茶甲酸化公CD的分子识别性能作了研究,结果显示3一位修饰CD（3一氧一八茶甲酸基一只CD）1对客体（环己醇）的包结性能是6一位修饰CD（6一氧一界禁甲酸基一八CD）2的4．4倍·结果还显示用环乙烷作客体时与主体正的包结和用…     

Über Tris(siloxymethyl)-, Tris(silylmercaptomethyl)- und Tris(silylmethyl)amine

By the reaction of alkali salts of triorgano-silanols, -silanethiols and trimethylsilylmethanol as well as of triorganosilyllithium compounds with tris(chloromethyl)amine, silyl derivatives of tris(hydroxymethyl)-, tris(mercaptomethyl)- and tris(methyl)amine were prepared.     

钴(II)-联吡啶-α-氨基酸的热力学和动力学研究

关于联吡啶为第一配体的二元、三元配合物的热力学和动力学性质的研究,以铜（Ⅱ）作为中心离子最为多见,而以钴（Ⅱ）作为中心离子的报导较少．实验表明,过渡金属钻（Ⅱ）能与大多数的生物配体、大π共轭体系形成相当稳定的二元、三元配合物,是生物功能模拟的一个具有应用价值的中心离子·钴（Ⅱ）卟啉可以代替铁（Ⅱ）卟啉,模拟血红蛋白、肌红蛋白[1],在生物体内起到输送氧的作用．为了充分了解钴（Ⅱ）与生物配体的配伍能力、配位方式以及其配位过程的动态行为,为推动钴（Ⅱ）配合物及其生物功能的模拟研究,本文分别采用PH电位法…     

A Tris(trifluoromethyl)antimony Adduct of a Nucleophilic Carbene: Geometric Distortions in Carbene Adducts

The synthesis, characterization and solid state structure are described for a reversed ylide, derived from 1,3-dimesityl-4,5-dichloroimidazol-2-ylidene and tris(trifluoromethyl)antimony. This carbene · stibine adduct is the first example of the 10-Sb-4 bonding arrangement in which only carbons are bound to antimony. The adduct has an Sb–C_(carbene) bond length of 282.1 pm, and a remarkable offset (19°) of the Sb–C_(carbene) bond from the pseudo-C₂ axis which passes through the imidazole fragment. A rather weak antimony-carbene interaction is suggested by this geometric distortion and is further supported by variable temperature ¹⁹F NMR experiments and solvent dependencies of chemical shifts.     

Synergic extraction of lanthanoids(III) with thenoyl trifluoroacetone and terpyridine

The synergic extraction of trivalent lanthanoids (Ln: La, Nd, Sm, Eu, Yb and Lu) with 2-thenoyltrifluoroacetone (Htta) and 2,26, 2-terpyridine (tpy) into benzene has been studied. The partition coefficient (P_s) of tpy was obtained experimentally in order to calculate the equilibrium concentration of tpy in the organic phase. From the slope analysis, it was shown that these lanthanoids were extracted as Ln(tta)₃(tpy). The adduct formation constant (_s,1) and the synergic extraction constant were obtained for each lanthanoid. The (_s,1) decreases with increasing atomic number of lanthanoids and the trend of (_s,1) is compared with that for bidentate and unidentate heterocyclic amines.     

Synthesis,Spectroscopic Studies,and Antifungal Activity of Tris(O-Alkyl or O-Aryltrithiophosphato) Aluminum(III)

Abstract

Aluminum(III) derivatives of O-alkyl or O-aryl trithiophosphate of the type Al[S₂P(SH)OR]₃ (R = Me, Et, Prⁱ, Buⁱ, Ph, CH₂Ph) have been synthesized. The products were obtained as white powdery solids. The monomers are soluble in common organic solvents and were characterized by elemental analyses, molecular weight determinations, and IR and (¹H, ²⁷Al, and ³¹P) NMR spectroscopic studies, which are consistent with six coordinated aluminum and bidentate behavior of the trithiophosphate moiety. The products also exhibit antifungal effectiveness against powdery mildew disease.     

Homoleptic 12-coordinate lanthanoids with eta(2)-nitroso ligands

The complexes [Et(4)N](3)[Ln(eta(2)-dcnm)(6)] (Ln = La, Ce, Nd, Gd, dcnm = dicyanonitrosomethanide) have discrete N, O 12-coordination owing to symmetrical chelation of the nitroso donor groups.     

(-)-N-芳硫基樟脑内磺酰胺的合成及其与β-酮酯的反应

(1S)-(-)-2,10-樟脑内磺酰胺与原位生成的芳基硫氯反应,制得系列亲电性N-芳硫基樟脑内磺酰胺试剂（1a~1c）,并将其应用于与β-酮酯活泼氢的不对称亲电取代反应,合成了具有光学活性的α-芳硫基-β-酮酯衍生物。考察了试剂结构、底物酯基的体积及环大小、添加剂种类及用量,以及溶剂、温度等反应条件对手性诱导效率的影响。初步实验结果表明：以(1S)-(-)-N-对甲基苯硫基樟脑内磺酰胺（1a）为亲电试剂,六元环β-酮甲酯为底物,甲苯为溶剂,碳酸钾为碱,室温反应48 h,α-芳硫基-β-酮酯的收率可达91%,对映选择性达40%ee。     

铁(III)卟啉催化β-胡萝卜素分解动力学研究

使用BeckmannDU-8B紫外可见分光光度计研究了以氯合四－间三甲苯基卟啉铁（Ⅲ）（FeTMPCl）为催化剂，间氯过氧化苯甲酸（mCPBA）为氧化剂，咪唑（I_m）、2－甲基咪唑（MeI_m）、2－乙基－4－甲基咪唑（EMI_m）为轴向配体，催化β-胡萝卜素（β－cte）氧化分解为维生素A的动力学规律，提出了反应机理，研究了温度、催化剂浓度、氧化剂浓度及轴向配体对反应速率的影响，应用Gauss－Newton－Marquardt方法求得各基元反应的有关动力学参数．