锌（Ⅱ）与2,2‘—联吡啶胺（dpa）和3—苯丙酸（HPPr）混配配合物的合成,晶 …

合成了锌（Ⅱ）与２，２’－联吡啶胺和３－苯丙酸混配配合物「Ｚｎ（ｄｐａ）（ＰＰｒ）２」．２Ｈ２Ｏ，并测定其晶体结构。晶体属三斜晶系，Ｐ１空间群，晶胞参数ａ＝１０．５４１（１）ｎｍ，ｂ＝１１．３３３（１）ｎｍ，ｃ＝１１．６９８（１）ｎｍ，     

一经式异构体[Co(N-(3-Aminopropyl)-1,3-propanediamine)(1,2-diamino-2-methylpropane)Cl][ZnCl4]·2H2O的合成及晶体结构

用过氧化物法合成了新体系［ Ｃｏ（ ３, ３－ｔｒｉ）（ ｉｂｎ） ＣＩ］［ ＺｎＣｌ４］（ ３, ３－ｔｒｉ＝ Ｎ－（ ３－Ａｍｉｎｏｐｒｏｐｙｌ）－ １, ３－ｐｒｏｐａｎｅｄｉａ－ｍｉｎｅ; ｉｂｎ＝１, ２－ｄｉａｍｉｎｏ－２－ｍｅｔｈｙｌｐｒｏｐａｎｅ）中的一经式异构体［Ｃｏ（３, ３ｔｒｉ）（ｉｂｎ）ＣＩ］［ＺｎＣｌ４］·２Ｈ２Ｏ,解析了其晶体结构。晶体学参数：三斜晶系,空间群Ｐ１（＃２）,ａ＝９９．５８（２）ｎｍ,ｂ＝１１４．８３（２）ｎｍ,ｃ＝９８．８１（１）ｎｍ,ａ＝９６．７９（２）°,β＝９７．２４３（１０）°,ｙ＝９６．８９（１）°,Ｖ＝１．１０５５（３）Ｘ １０６ｎｍ３,Ｄｅ＝１．６７８ｇ·ｃｍ－３,Ｚ＝２,Ｆ０００＝５７２．００,μ（ Ｍｏ Ｋａ）＝ ２４． ５９ｃｍ－１, Ｒ＝ ０． ０２５, Ｒｗ＝ ０． ０３４。晶胞中含 ２个配位阳离子, ２个 ［ＺｎＣｌ４］２－阴离子及 ４个水分子。     

铜(Ⅱ)与苯基羧酸(HPCA)和2,2''''-联吡啶衍生物(dpx)混配配合物的合成和表征

合成了铜（Ⅱ）与苯基羧酸根［ＰＣＡ－＝苯甲酸根（Ｂｚ－），２－苯乙酸根（ＰＡｃ－），３－苯丙酸根（ＰＰｒ－），４－苯丁酸根［ＰＢｕ－）］和２，２′－联吡啶衍生物（ｄｐｘ：２，２′－联吡啶胺ｄｐａ、２，２′－联吡啶酮ｄｐｋ、２，２′－联吡啶甲烷ｄｐｍ）三大系列１２种新的三元配合物。用元素分析、摩尔电导、红外光谱、１Ｈ核磁共振、差热分析等实验方法表征了它们的组成和性质。确定该系列配合物化学组成为Ｃｕ（ＰＣＡ）２（ｄｐａ）、Ｃｕ（ＰＣＡ）２（ｄｐｍ）、Ｃｕ（ＰＣＡ）２（ｄｐｋ）·ｎＨ２Ｏ（ｎ＝２－４）。它们具有相似的组成和配位方式。它们的可能结构为：二个ＰＣＡ－与Ｃｕ（Ⅱ）单齿配位，一个ｄｐｘ与Ｃｕ（Ⅱ）Ｎ，Ｎ二齿螯合配位。ｄｐｋ的羰基在金属离子Ｃｕ２＋的存在下发生水化作用成ｄｐｋ·Ｈ２Ｏ。用１ＨＮＭＲ法研究了Ｃｕ（Ｂｚ）２（ｄｐｘ）·ｎＨ２Ｏ和Ｃｕ（ＰＡｃ）２（ｄｐｘ）·ｎＨ２Ｏ二个体系其分子内或分子间可能存在的非共价键作用。     

μ-氧桥联的双核铜(Ⅱ)配合物Cu2(Salen)2的合成、结构和光谱性质

报道了双核铜（Ⅱ）配合物Ｃｕ２（Ｓａｌｅｎ）２（Ｓａｌｅｎ为Ｎ,Ｎ′－二水杨醛乙二胺席夫碱）的合成、表征和晶体结构分析．该晶体属单斜晶系,具有Ｃ２／ｃ（Ｎｏ．１５）空间群,ａ＝２．６５８０（５）ｎｍ,ｂ＝０．６９８６（１）ｎｍ,ｃ＝１．４７１８（３）ｎｍ,β＝９７．６３（３）°,Ｖ＝２．７０８（１）ｎｍ３,Ｚ＝８,Ｄｃ＝１．６１８Ｍｇ／ｍ３,Ｆ（０００）＝１３５２,Ｒ＝０．０８８,ｗＲ＝０．０７３,ＧＯＦ（Ｆ）＝０．８９．该化合物是由两个氧桥桥联的双核铜（Ⅱ）配合物,铜（Ⅱ）离子处于五配位的畸变四方锥配位环境中报道了双核铜（Ⅱ）配合物Ｃｕ２（Ｓａｌｅｎ）２（Ｓａｌｅｎ为Ｎ,Ｎ′－二水杨醛乙二胺席夫碱）的合成、表征和晶体结构分析．该晶体属单斜晶系,具有Ｃ２／ｃ（Ｎｏ．１５）空间群,ａ＝２．６５８０（５）ｎｍ,ｂ＝０．６９８６（１）ｎｍ,ｃ＝１．４７１８（３）ｎｍ,β＝９７．６３（３）°,Ｖ＝２．７０８（１）ｎｍ３,Ｚ＝８,Ｄｃ＝１．６１８Ｍｇ／ｍ３,Ｆ（０００）＝１３５２,Ｒ＝０．０８８,ｗＲ＝０．０７３,ＧＯＦ（Ｆ）＝０．８９．该化合物是由两个氧桥桥联的双核铜（Ⅱ）配合物,铜（Ⅱ）离子处于五配位的畸变四方锥     

新试剂1-(6-硝基-2-苯并噻唑)-3-(4-硝基苯)-三氮烯与锌的显色反应研究及应用

研究了新显色剂１－（６－硝基－２－苯并噻唑）－３－（４－硝基苯）－三氮烯（ＮＢＴＮＰＴ）与锌的显色反应，在非离子表面活性剂ＴｒｉｔｏｎＸ－１００存在下，ｐＨ１０．１～１０．８的Ｎａ２Ｂ４Ｏ７－ＮａＯＨ缓冲溶液中，Ｚｎ２＋与试剂能形成１∶２的橙黄色配合物，最大吸收波长为４４６ｎｍ，同时在５２８ｎｍ处配合物表现有最大负吸收，其表观摩尔吸光系数分别为ε＝７．０３×１０４Ｌ·ｍｏｌ－１·ｃｍ－１和ε＝１．０６×１０５Ｌ·ｍｏｌ－１·ｃｍ－１．用拟定的方法测定了人发和婴儿奶粉中的微量锌，结果令人满意．     

具有不同类型桥基的双核Cu(Ⅱ)-Schiff碱配合物的合成和晶体结构

合成了３个分别以Ｃ２Ｏ２－４（［Ｃｕ２（Ｌ１）２（ｏｘ）］，１），ＡｃＯ－（［Ｃｕ２（ＡｃＯ）（Ｌ２）２］ＢＦ４，２）和酚氧（［Ｃｕ２（Ｌ３）２］（ＣｌＯ４）２，３）为桥基的双核铜配合物，并测定了１的复配合物［Ｃｕ２（Ｌ１）２（ｏｘ）］·［Ｆｅ（ＯＨ）２（Ｈ２Ｏ）４］ＣｌＯ４·Ｈ２Ｏ（１′）及２和３的晶体结构．Ｘ射线衍射结果表明：１′，２和３分别属于Ｆｄｄｄ，Ｐ２１／ｃ和Ｐ２１／ｃ空间群．晶胞参数：［Ｃｕ２（Ｌ１）２（ｏｘ）］［Ｆｅ（ＯＨ）２（Ｈ２Ｏ）４］ＣｌＯ４·Ｈ２Ｏ，ａ＝２．４３９０（４）ｎｍ，ｂ＝３．０５３８（６）ｎｍ，ｃ＝１．８４９４（６）ｎｍ，α＝β＝γ＝９０．００°；２，ａ＝０．８４７（１）ｎｍ，ｂ＝２．６５４２（８）ｎｍ，ｃ＝１．４１００（６）ｎｍ，β＝９１．３４（６）°；３，ａ＝０．７６４６（３）ｎｍ，ｂ＝１．６９８３（３）ｎｍ，ｃ＝２．４４１７（３）ｎｍ，β＝９７．１１°     

N-(2-对甲苯磺酰胺基乙基)氮杂12-冠-4合碘化氯仿的合成及晶体结构

Ｎ－（２－对甲苯磺酰胺基乙基）氮杂１２－冠－４（Ａ）与碘在氯仿溶液中反应，得到了电荷转移配合物Ａ·［ＩＨＣＣｌ３］晶体．Ｉ…Ｈ—Ｃ氢键的键长为０．３８９ｎｍ．晶体属单斜晶系，空间群Ｐ２１／ｎ，ａ＝０．７３６４（７）ｎｍ，ｂ＝１．６７３２（０）ｎｍ，ｃ＝２．１４１３（６）ｎｍ，β＝９９．０９（１）°，Ｚ＝４，Ｖ＝２．６０５５（５）ｎｍ３，Ｒ１＝０．０４７９，Ｒ２＝０．０４２４     

Eu2(3,4-DMBA)6(PHEN)2的晶体结构及HRS研究

合成了铕（Ⅲ）与３,４－二甲基苯甲酸（３,４－ＨＤＭＢＡ）、邻菲咯啉（ＰＨＥＮ）形成的晶体配合物Ｅｕ２（３,４－ＤＭＢＡ）６（ＰＨＥＮ）２．测定其分子量Ｍ＝１５５９．３５,晶体属三斜晶系,Ｐ１空间群,ａ＝１．２６６５（４）ｎｍ,ｂ＝１．３５６７（４）ｎｍ,ｃ＝１．０７５５（４）ｎｍ,α＝９８．８７（３）°,β＝１０８．２５（３）°,γ＝８７．９８（２）°,Ｚ＝１,最终的偏离因子Ｒ＝０．０３１．以Ｅｕ（Ⅲ）离子为荧光探针,在７７Ｋ下测定了配合物的高分辨光谱（ＨＲＳ）．铕配合物的激发光谱、发光光谱、时间分辨光谱和发光寿命测定结果表明,该配合物中存在两种化学环境不同的Ｅｕ（Ⅲ）离子格位     

罗丹明B合锌（Ⅱ）配合物的合成,分子结构与性质研究

合成了ＲＢ－Ｚｎ配合物,晶体结构分析结果表明配合物组成为「Ｚｎ（ＲＢ）（ＯＡｃ）２（Ｈ２Ｏ）」晶体属单斜晶系、空间群为Ｐ２１／ｎ（＃１４）,晶胞参数为ａ＝１．０２９８（２）ｎｍ,ｂ＝１．８９０１（４）ｎｍ,ｃ＝１．６６６０（６）ｎｍ;β＝１０５．２４（３）°;Ｚ＝４,Ｄｃａｌ＝１．３６７ｇ／ｃｍ＾３。研究了配合物的物质的量电导,ＩＲ和荧光光谱,同时对配体配合物的半导体行为进行了考察。     

β—烷氧羰乙基三氯化锡与2—羟基苯乙酮缩苯胺类Schiff碱配合…

合成并表征了１６种新的β－烷氧羰乙基三氯化锡与２－羟基苯乙酮缩苯胺类Ｓｃｈｉｆｆ碱配合物，测定了β－甲氧羰乙基三氯化锡与２－羟基苯乙酮缩对甲苯胺Ｓｃｈｉｆｆ碱配合物的晶体结构。晶体属于Ｐ１空间群，晶胞参数：ａ＝１．０２０１（６）ｎｍ，ｂ＝１．０８２２（４）ｎｍ，ｃ＝１．３９４９（６）ｎｍ，ａ＝９９．８８（３）°，β＝９８．６３（４）°，γ＝９７．８６（４）°，Ｚ＝２。配合物是配体通过酚羟基氧原子与     

Sc2MgGa2 and Y2MgGa2

Scandium magnesium gallide, Sc₂MgGa₂, and yttrium magnesium gallide, Y₂MgGa₂, were synthesized from the corresponding elements by heating under an argon atmosphere in an induction furnace. These intermetallic compounds crystallize in the tetragonal Mo₂FeB₂‐type structure. All three crystallographically unique atoms occupy special positions and the site symmetries of (Sc/Y, Ga) and Mg are m2m and 4/m, respectively. The coordinations around Sc/Y, Mg and Ga are pentagonal (Sc/Y), tetragonal (Mg) and triangular (Ga) prisms, with four (Mg) or three (Ga) additional capping atoms leading to the coordination numbers [10], [8+4] and [6+3], respectively. The crystal structure of Sc₂MgGa₂ was determined from single‐crystal diffraction intensities and the isostructural Y₂MgGa₂ was identified from powder diffraction data.     

Zur Kenntnis der Dialkalimetalldichalkogenide β-Na2S2, K2S2, α-Rb2S2, β-Rb2S2, K2Se2, Rb2Se2, α-K2Te2, β-K2Te2 und Rb2Te2

On Dialkali Metal Dichalcogenides β-Na₂S₂, K₂S₂, α-Rb₂S₂, β-Rb₂S₂, K₂Se₂, Rb₂Se₂, α-K₂Te₂, β-K₂Te₂ and Rb₂Te₂ The first presentation of pure samples of α- and β-Rb₂S₂, α- and β-K₂Te₂, and Rb₂Te₂ is described. Using single crystals of K₂S₂ and K₂Se₂, received by ammonothermal synthesis, the structure of the Na₂O₂ type and by using single crystals of β-Na₂S₂ and β-K₂Te₂ the Li₂O₂ type structure will be refined. By combined investigations with temperature-dependent Guinier-, neutron diffraction-, thermal analysis, and Raman-spectroscopy the nature of the monotropic phase transition from the Na₂O₂ type to the Li₂O₂ type will be explained by means of the examples α-/β-Na₂S₂ and α-/β-K₂Te₂. A further case of dimorphic condition as well as the monotropic phase transition of α- and β-Rb₂S₂ is presented. The existing areas of the structure fields of the dialkali metal dichalcogenides are limited by the model of the polar covalence.     

Crystal Structures of [Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2. Raman Spectra of [Ph2Sn(O2PPh2)2] and [PhClSn(O2PPh2)OMe]2

[(n‐Bu)₂Sn(O₂PPh₂)₂] ( 1 ), and [Ph₂Sn(O₂PPh₂)₂] ( 2 ) have been synthesized by the reactions of R₂SnCl₂ (R=n‐Bu, Ph) with HO₂PPh₂ in Methanol. From the reaction of Ph₂SnCl₂ with diphenylphosphinic acid a third product [PhClSn(O₂PPh₂)OMe]₂ ( 3 ) could be isolated. X‐ray diffraction studies show 1 to crystallize in the monoclinic space group P2₁/c with a = 1303.7(1) pm, b = 2286.9(2) pm, c = 1063.1(1) pm, β = 94.383(6)°, and Z = 4. 2 crystallizes triclinic in the space group , the cell parameters being a = 1293.2(2) pm, b = 1478.5(4) pm, c = 1507.2(3) pm, α = 98.86(3)°, β = 109.63(2)°, γ = 114.88(2)°, and Z = 2. Both compounds form arrays of eight‐membered rings (SnOPO)₂ linked at the tin atoms to form chains of infinite length. The dimer 3 consists of a like ring, in which the tin atoms are bridged by methoxo groups. It crystallizes triclinic in space group with a = 946.4(1) pm, b = 963.7(1) pm, c = 1174.2(1) pm, α = 82.495(6)°, β = 66.451(6)°, γ = 74.922(6)°, and Z = 1 for the dimer. The Raman spectra of 2 and 3 are given and discussed.     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

Syntheses,Spectroscopic Studies,and Crystal Structures of Me2Sn(O2PPh2)2, Ph2Pb(O2PMe2)2, and Ph2Pb(O2PPh2)2

Me₂Sn(O₂PPh₂)₂ ( 1 ), Ph₂Pb(O₂PMe₂)₂ ( 2 ), and Ph₂Pb(O₂PPh₂)₂ ( 3 ) have been synthesized by the reactions of Me₂SnCl₂ or Ph₃PbCl with the corresponding diorganophosphinic acid in methanol. X‐ray diffraction studies show that the diorganophosphinate groups behave as double bridges between the metal atoms leading to polymeric ring‐chain structures with M₂O₄P₂ (M = Pb, Sn) eight‐membered rings. The organic groups bonded to the metal atoms are in trans‐position in the resulting octahedral arrangement around the metal atoms. The IR and the mass spectra were reported and discussed.     

Thermal decomposition of Me3SnO2PCl2, Me2Sn(O2PCl2)2 and Ph3SnO2PCl2

TG and DTA studies on Me₃SnO₂PCl₂, Me₂Sn(O₂PCl₂)₂ and Ph₃SnO₂PCl₂ were carried out under dynamic argon atmosphere. The results show that the decomposition proceeds in different stages leading to the formation of Sn₃(PO₄)₂ as a stable product. This compound was characterized by IR spectroscopy. Decomposition schemes involving reductive elimination reactions were proposed.     

The alkali hypophosphites KH2PO2, RbH2PO2 and CsH2PO2

The structures of the hypophosphites KH₂PO₂ (potassium hypophosphite), RbH₂PO₂ (rubidium hypophosphite) and CsH₂PO₂ (caesium hypophosphite) have been determined by single‐crystal X‐ray diffraction. The structures consist of layers of alkali cations and hypophosphite anions, with the latter bridging four cations within the same layer. The Rb and Cs hypophosphites are isomorphous.