一种合成平面双核金属酞菁的新方法

A new planar binuclear bisphthalocyaninato-metal-planar hexa-tert-butylbisphthalocyaninato dicobalt (Ⅱ) was synthesized by the reaction of 4-tert-butylphthalic anhydride with pyromellitic dianhydride, urea and CoCl₂·6H₂O. This is a new synthesis method (phthalic route). The total yield reaches up to 15%. The synthetic reaction conditions are as follows: appropriate molar ratio of the reactant, reaction in solid phase and without ammonium molybdate as catalyst.     

A POTENTIOMETRIC STUDY OF METAL CHELATES WITH TETRAETHYLENEPENTAAMINEHEPTA-ACETIC ACID

Abstract

The protonation constants of tetraethylenepentaamineheptaacetic acid, TPHA, were determined by potentiometric titration in aqueous solution at an ionic strength of 0.10 M KNO₃ and at 25°C. The formation constants of various metal-TPHA complexes were also obtained by titrating mixtures of metal to ligand in molar ratios of 1 :1 and 2:1. Calculations were performed with the computer program BEST. Individual stability constants are reported for Co(II). Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II) with TPHA as well as their related pro-tonated species. The stabilities of the 1:1 complexes parallel to those of similar complexes with DTPA and TTHA. However the 2: 1 complexes have significantly larger log K _ML's than their TTHA counterparts. The extra stability of the 2:1 metal-TPHA complexes is explained in terms of ligand denticity and steric effects. Mercury(II)-TPHA complexes exhibited the highest formation constants and the copper-TPHA complexes had slightly higher log K _ML's than those for Co(II), Ni(II), Zn(II), Cd(II) and Pb(II).     

双核铜酶的化学模拟

本文综述了双核铜酶,特别是酪氨酸酶、血蓝蛋白的结构,键合氧、活化氧的性能及有关仿酶模型的研究进展。     

SYNTHESIS OF 5-DODECANOYLAMINE-8-HYDROXY-1,4-NAPHTHOQUINONE AND STUDY OF SOME OF ITS BIVALENT METAL CHELATES

Abstract

Two new naphthoquinone derivatives, 5-dodecanoylamine-8-hydroxy-l,4-naphthoquinone (1) and 5-dodecanoylamine-8-acetoxy-l,4-naphthoquinone (2), have been prepared and characterized. Their chelating ability with Ni(II) and Co(II) have been studied. Compound (1) coordinates to the divalent metal ions as a monoanionic bidentate ligand. The complexes were found to contain two ligands and two molecules of coordinated water. The structure and bonding of the chelates are discussed based on the spectroscopic data.     

Synthesis and spectroscopic studies of novel mononuclear and binuclear ruthenium(III) complexes with bidentate and tridentate acyclic hydrazones

Nine novel acyclic hydrazone ligands, FINH?=?N-(furylidene)-N′-isonicotinoylhydrazine, FNH?=?N-(furylidene)-N′-nicotinoylhydrazine, PINH?=?N-(pyrienylidene)-N′-isonicotinoylhydrazine, PNH?=?N-(pyrienylidene)-N′-nicotinoylhydrazine, TINH?=?N-(thienylidene)-N′-isonicotinoylhydrazine, TNH?=?N-(thienylidene)-N′-nicotinoylhydrazine, FSH?=?N-(furylidene)-N′-salicyloylhydrazine, PSH?=?N-(pyrienylidene)-N′-salicyloylhydrazine and TSH?=?N-(thienylidene)-N′-salicyloylhydrazine, have been synthesized. Their corresponding mononuclear and binuclear ruthenium(III) complexes have been prepared by the reaction of the ligand with RuCl₃·3H₂O in 1?:?2 and 2?:?2 molar ratio and are characterized by elemental analyses, thermogravimetric analyses (TGA and DTG), IR, electronic, magnetic susceptibility and electrical conductance measurements. Electronic spectra and magnetic susceptibility measurements of the solid complexes (both mono- and binuclear) indicate an octahedral geometry around ruthenium(III). Particular emphasis is given to the binuclear complexes in which FSH, PSH and TSH behave as tridentate ligands and chloride bridges the Ru(III) ions. Conductance measurements show the mononuclear complexes are electrolytic and binuclear complexes are of non-electrolytic. The fungicidal activities of the ligands and metal complexes against Fusarium oxysporium and Aspergillus niger are described.     

过渡金属乙酰丙酮螯合物的体积排除色谱研究

用体积排除色谱方法研究了过渡金属Fe(Ⅲ)、Co(Ⅲ)、Cu(Ⅱ)、Ni(Ⅱ)的乙酰丙酮螯合物在四氢呋喃溶液中的加合和缔合行为。在溶液中乙酰丙酮钴(Ⅲ)以单个螯合物分子的形式存在,乙酰丙酮铜(Ⅱ)和乙酰丙酮铁(Ⅲ)与溶剂加合生成加合物,乙酰丙酮铁(Ⅲ)除加合物外还存在缔合度为2-10的多分散缔合物,乙酰丙酮镍(Ⅱ)水合物在四氢呋喃中产生了加合交换作用,同时存在缔合度为6左右的缔合物。色谱数据给出了螯合物、加合物及缔合物的相对含量。螯合物与相同分子量的聚苯乙烯相比,其保留体积的滞后以Ni相似文献   

过渡金属乙酰丙酮螯合物的体积排除色谱研究

用定量体积排除色谱方法研究了过渡金属Fe(Ⅲ)、Co(Ⅲ)、Cu(Ⅱ)、Ni(Ⅱ)的乙酰丙酮螯合物在四氢呋喃溶液中的加合和缔合行为。在溶液中乙酰丙酮钴(Ⅲ)以单个螯合物分子的形式存在,乙酰丙酮铜(Ⅱ)和乙酰丙酮铁(Ⅲ)与溶剂加合生成加合物,乙酰丙酮铁(Ⅲ)除加合物外还存在缔合度为2-10的多分散缔合物,乙酰丙酮镍(Ⅱ)水合物在四氢呋喃中产生了加合交换作用,同时存在缔合度为6左右的缔合物。色谱数据给出了螯合物、加合物及缔合物     

A POTENTIOMETRIC STUDY OF METAL CHELATES WITH PENTAETHYLENEHEXAAMINEOCTAACETIC ACID

Abstract

The protonation constants of pentaethylenehexaamineoctaacetic acid, PHOA, were determined by potentiometric titration in aqueous solution at an ionic strength of 0.10 M KNO₃ and at 25°C. The formation constants of various metal-PHOA complexes were also obtained by titrating mixtures of metal to ligand in molar ratios of 1:1 and 2:1. Calculations were performed with the computer program BEST. Individual formation constants are reported for Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II) with PHOA as well as their related protonated species. The stabilities of the 1:1 and 2:1 complexes are similar in many respects to complexes formed with tetraethylenepentaamineheptaacetic acid (TPHA). The similarities in the stabilities of both the 1:1 and 2:1 complexes with PHOA and those with TPHA are explained in terms of ligand denticity and steric effects. Mercury(II)-PHOA complexes exhibited the highest formation constants, followed by copper(II)-PHOA complexes which had higher log K _ML's than those for Co(II), Ni(II), Zn(II), Cd(II) and Pb(II).     

2，6─二甲酸─4─取代苯酚双缩苯甲酰肼双核铜（Ⅱ）配合物的合成与磁性

本文合成并表征了两个新的双核铜（Ⅱ）配合物：〔Ｃｕ２（Ｌ）（μ─Ｃｌ）Ｃｌ２〕，配体Ｌ为２，６─二甲酰─４─甲基苯酚双缩苯甲酰肼，取代基分别为氯（Ｌ１）和叔丁基（Ｌ２）．配合物具有相同的组成和配位构型．变温磁化率（４－３００Ｋ）测定结果表明，由于取代基不同，其磁交换参数分别为－４６．２ｃｍ（－１）（Ｌ１）和－５７．６ｃｍ（－１）（Ｌ２）．     

ADDUCTS OF THEOBROMINE WITH 3d METAL PERCHLORATES

Abstract

Adducts of theobromine (tbH) with 3d metal perchlorates (Mⁿ⁺ = Cr^3-. Mn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn^2- I here prepared by refluxing mixtures of the Iigand and a metal salt in ethyl acetate-triethyl orthoformate. The new complexes invariably involve 2: 1 molar ratios of tbH to metal ion and are apparently monomeric with terminal tbH ligands binding riaa ring nitrogen (N9 or Nl). The Mn²⁺, Cu²⁺ and Zn^2- complexes are distorted tetrahedral, involving tuo tbH and two unidentate perchlorato ligands in the first coordination sphere of the metal ion. The remaining metal(II) complexes (Fe, Co, Ni) were obtained as monohydrates. These compounds are pentacoordinated of the [M(tbH)₂(OClO₃)₂(OH₂)] type, containing one aqua ligand in addition to the tbH and perchlorato ligands. The Cr³⁺ and Fe³⁺ complexes are low-symmetry hexacoordinated, with two tbH ligands. two unidentate and one bidentate chelating perchlorate Iigands.     

二(1,3-二硫杂环戊烯-2-硫酮-4,5-二巯基)镉-季铵类配合物的合成与表征

二（１，３－二硫杂环戊烯－２－硫酮－４，５－二巯基）镉－季铵类配合物的合成与表征李洪启宋燕西＊周宏英王爱勤姚钟麒俞贤达（中国科学院兰州化学物理研究所，兰州７３００００；＊兰州大学化学系，兰州７３００００）关键词二（１，３－二硫杂环戊烯－２－硫酮－４，...     

μ－邻苯二甲酸希土与5－硝基－1，10－菲咯啉双核配合物的合成、光谱、磁性

本文合成了四个以邻苯二甲酸阴离子为桥联配体的新型希土双核配合物［Ｌｎ２（Ｐｈｔｈ）（ＮＯ２－ｐｈｅｎ）４］（ＣｌＯ４）４·ｘＨ２Ｏ［Ｌｎ＝Ｇｄ、Ｔｂ、Ｈｏ、Ｅｒ，ＮＯ２－Ｐｈｅｎ＝５－硝基－１，１０－菲咯啉，Ｐｈｔｈ＝邻苯二甲酸阴离子）．经元素分析，ＩＲ、电导、电子吸收光谱，表征了配合物，测定了［Ｇｄ２（Ｐｈｔｈ）（ＮＯ２－ｐｈｅｎ）４］（ＣｌＯ４）４·４Ｈ２Ｏ的变温磁化率（４～３００Ｋ），其数值用最小二乘法与理论方程拟合，求得交换参数Ｊ＝－２．１８ｃｍ－１，表明Ｇｄ（Ⅲ）－Ｇｄ（Ⅲ）离子间存在较弱的反铁磁交换相互作用．     

METAL CHELATES OF NEW LIGANDS: 1,2-BENZOTHIAZINE-1,1-DIOXIDE DERIVATIVES

Abstract

The novel chelates ML₂ (M = Co, Ni, Cu, Zn) were obtained by the interaction of 3-benzoyl-4-hydroxy-1,2-benzothiazine-4(3H)-on-1,1-dioxide and 2-methyl-3-benzoyl-4-hydroxy-1,2-benzo-thiazine-4(3H)-on-1,1-dioxide with elemental metals (direct electrochemical synthesis) or their acetates (chemical synthesis) in methanol. The tetrahedral or polymeric-octahedral structures with a β-diketonate fragment are assigned based on IR and ¹H NMR spectra. The studied ligands and their complexes are model compounds of molecules used as anti-inflammatory drugs.     

二茂铁基苯酰腙的d区金属螯合物的合成和表征

二茂铁基苯酰腙与d区金属乙酸盐或氯化物在乙醇中反应,得到了6个新的螯合物,分子式为M(Fcbh)n[Fcbh=Fc—C=N—N=C-C_6H_5,Fc=C_5H_5—FeC_5H_4;M=Cr(Ⅲ)、Fe(Ⅲ)时,n=3;M=Mn(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)时,n=2]和Pd(Fcbh—H)_2Cl_2[Fcbh—H=Fc—C=N—NHCOC_6H_5]通过元素分析,红外光谱,H核磁共振谱和质谱,确定了螯合物的组成和结构。描述了二茂铁基苯酰腙配体与d区金属的两种不同的配位方式。     

2, 6─二甲酸─4─取代苯酚双缩苯甲酰肼双核铜(Ⅱ)配合物的合成与磁性

本文合成并表征了两个新的双核铜（Ⅱ）配合物：［Ｃｕ２（Ｌ）（μ－Ｃｌ）Ｃｌ２］，配体Ｌ为２，６－二甲酰－４－基苯酚双缩苯甲酰肼，取代基分别为氯（Ｌ１）和叔丁基（Ｌ２）。配合物具有相同的组成和配位构型。变温磁化率测定结果表明，由于取代基不同，其磁交换参数分别为－４６．２ｃｍ＾－１（Ｌ１）和－５７．６ｃｍ＾－１（Ｌ２）。     

Asymmetric Synthesis of Novel Ferrocenyl Ligands with Planar and Central Chirality

A stereogenic center at the position β to the metallocene backbone is present in ferrocenyl ligands 2 , which are interesting for asymmetric catalysis. These planar-chiral compounds are accessible for the first time by a highly diastereoselective and enantioselective synthesis (de=93–97 %; ee≥96 %) from the ferrocenyl ketones 1 . A variety of donor groups (E¹=Ph₂P⋅BH₃, SMe, SiPr; E²=SMe, STol, SePh, Ph₂P⋅BH₃, iPr₂P⋅BH₃) can be introduced as electrophiles. Tol=tolyl=CH₃C₆H₄.     

μ-邻苯二甲酸希土与5-硝基-1,10-菲咯啉双核配合物的合成、光谱、磁性

本文合成了四个以邻苯二甲酸阴离子为桥联配体的新型希土双核配合物［Ｌｎ２（Ｐｈｔｈ）（ＮＯ２－ｐｈｅｎ）４］（ＣｌＯ４）４．ｘＨ２Ｏ［Ｌｎ＝Ｇｄ，Ｈｏ，Ｅｒ，ＮＯ２－Ｐｈｅｎ＝５－硝基－１，１０－菲咯啉，Ｐｈｔｈ－邻苯二甲酸阴离子）。经元素分析，ＩＲ，电导，电子吸收光谱，表征了配合物，测定了［Ｇｄ２（ｐｈｔｈ）（ＮＯ２－ｐｈｅｎ）４］（ＣｌＯ４）４．４Ｈ２Ｏ的变温磁化率（４－３００Ｋ），其数值用最小     

Redox and Acid–Base Properties of Binuclear 4‐Terphenyldithiophenolate Complexes of Nickel

This work reports on the redox and acid–base properties of binuclear complexes of nickel from 1,4‐terphenyldithiophenol ligands. The results provide insight into the cooperative electronic interaction between a dinickel core and its ligand. Donor/acceptor contributions flexibly adjust to stabilize different redox states at the metals, which is relevant for redox reactions like proton reduction. Proton transfer to the [S₂Ni₂] core and Ni?H bond formation are kinetically favored over the thermodynamically favored yet unproductive proton transfer to ligand.     

Synthesis and characterization of new ferrocenyl bishydrazones

New ferrocenyl bishydrazones (2a–2d) have been efficiently obtained from 1,1′-ferrocenedicarboxaldehyde by a straightforward synthesis. The four new compounds have been fully characterized by NMR (¹H, ¹³C), high-resolution mass spectroscopy, and the molecular structure of compounds (2a–2d) has been elucidated by X-ray diffraction on single crystals.