镓在氨基吡啶树脂上的吸附行为及机理

前文已报道了氨基吡啶树脂对AuCl_4~-、PtCl_6~(2-)的吸附性。本文报道4-氨基吡啶树脂对镓的吸附行为与机理。在6mol/L HCl条件下,对镓的氯络阴离子(GaCl_4~-)有很好的吸附性。并能定量洗脱。测得静态吸附容量为351.15mg/g树脂,用化学法及红外光谱等方法,测得4-氨基吡啶树脂吸附镓(Ⅲ)的基本参数。     

Base-freie Tris(trimethylsilyl)methyl-Derivate des Lithiums,Aluminiums, Galliums und Indiums

Base-free Tris(trimethylsilyl)methyl Derivatives of Lithium, Aluminium, Gallium, and Indium Base-free LiR* (R*=-C(SiMe₃)₃) has been prepared from R*Cl and Li-metal in toluene at 85?90°C and used to synthesize the metallanes R*MMe₂ with M = Al, Ga and In, respectively. The NMR (¹H, ¹³C, ²⁹Si) and the vibrational spectra of these trisyl compounds have been discussed. AlCl₃ and LiR*(ratio 1 : 1) forms the metallate metallate Li[R*AlCl₃]. The triclinic unit cell (space group P1 ) consists of a centrosymmetric assoziate, formed by four Li[R*AlCl₃]- units with Al? Cl…?Li bridges, two pairs of Li-atoms differing in their chlorine-coordination and two disordered toluene molecules, inserted in the crystal lattice (R₁wR₂ =0,0444/0,1072). The reaction of GaCl₃ with LiR* (I :1) gives the unusual sesquichloride (R*Ga(Cl_1,33)Me_0,67)₃ in moderate yield. The X-ray structure determination shows a Ga₃Cl₃-skeleton with chairconformation and disordered, terminal gallium ligands (R₁/wR₂= 0,0646/0,2270).     

Gallium(III) halide-catalyzed coupling of indoles with phenylacetylene: synthesis of bis(indolyl)phenylethanes

Indoles undergo smooth coupling with phenylacetylene in the presence of 10 mol % of gallium(III) chloride or gallium(III) bromide under mild conditions to afford the corresponding 1,1-bis(1H-3-indolyl)-1-phenylethanes in high yields and with high selectivity.     

Ion-selective electrode for gallium determination in nickel alloy, fly-ash and biological samples

A poly(vinyl chloride)-based membrane of 2,9-dimethyl-4,11-diphenyl-1,5,8,12-tetraazacyclotetradeca-1,4,8,11-tetraene (DDTCT) with sodium tetraphenyl borate (STB) as an anion excluder and dibutyl phthalate (DBP), dibutyl butylphosphonate (DBBP), tris(2-ethylhexyl) phosphate (TEP) and tributyl phosphate (TBP) as plasticizing solvent mediators was prepared and investigated as a Ga(III)-selective electrode. The best performance was observed with the membrane having the ligand-PVC-DBP-STB composition 1:4:1:1, which worked well over a wide concentration range (1.45 × 10⁻⁶ to 0.1 mol L⁻¹) with a Nernstian slope of 28.7 mV per decade of activity between pH 4.0 and 10.0. This electrode showed a fast response time of 12 s and was used over a period of 100 days with good reproducibility (s = 0.3 mV). The selectivity coefficients for monovalent, divalent and trivalent cations indicate excellent selectivity for Ga(III) ions over a large number of cations. Anions such as Cl⁻ and SO₄²⁻ do not interfere and the electrode also works satisfactorily in partially water-alcohol medium. The practical utility of the membrane sensor has also been observed in solutions contaminated with detergents, i.e., cetyltrimethylammonium bromide and sodium dodecyl sulfate and used for the determination of gallium in nickel alloy, fly-ash and biological samples.     

镓(Ⅲ)-茜素红体系的吸附伏安法

本文对镓(Ⅲ)与茜素红络合物在悬汞电极上的吸附伏安法作了研究,确定了电极过程.在HAc-NH_4Ac(pH4.06)缓冲溶液中茜素红存在下,用1.5阶微分吸附伏安法测定镓,其线性范围是1×10~(-10)～1×10~(-7)mol/L,其检测限为1×10~(-10)mol/L,并用此法测定了中草药中的痕量镓.     

Solvothermal syntheses of Cu3P via reactions of amorphous red phosphorus with a variety of copper sources

Polycrystalline Cu₃P was successfully prepared under a wide variety of solvothermal conditions. The reaction of red phosphorus with several copper sources (copper metal, copper (I) iodide, copper (I) chloride and copper (II) chloride) at 150-200 °C for 1-2 days in water produced Cu₃P. Products were examined with powder X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. Thermal analyses and optical spectroscopy were also performed. A detailed list of reaction conditions, products and impurity phases (where applicable) are reported.     

Synthese und Charakterisierung neuer intramolekular stickstoffstabilisierter Organoaluminium‐ und Organogalliumalkoxide

Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me₂Al{μ‐O(CH₂)₃NMe₂}]₂ ( 1a ), Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6 ( 2a ), [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]₂ ( 3a ) and [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]₂ ( 4 ) are formed by reacting equimolar amounts of AlMe₃ and Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, (S)‐i‐PrNHCH(i‐Pr)CH₂OH, or (S)‐PhCH₂NHCH(i‐Pr)CH₂OH, respectively. An excess of AlMe₃ reacts with Me₂N(CH₂)₂OH, Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, and (S)‐i‐PrNHCH(i‐Pr)CH₂OH producing the “pick‐a‐back” complexes [Me₂AlO(CH₂)₂NMe₂](AlMe₃) ( 5 ), [Me₂AlO(CH₂)₃NMe₂](AlMe₃) ( 1b ), [Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6](AlMe₃)₂ ( 2b ), and [(S)‐Me₂AlOCH₂CH(i‐Pr)NH‐i‐Pr](AlMe₃) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 6 ) and [{CH₂=C(CH₃)}(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 8 ) are to obtain from Me₂AlCl and Me₂N(CH₂)₂OH and from [Cl₂Al{μ‐O(CH₂)₂NMe₂}]₂ ( 7 ) and CH₂=C(CH₃)MgBr, respectively. The analogous dimethylgallium alkoxides [Me₂Ga{μ‐O(CH₂)₃NMe₂}]₂ ( 9 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]_n ( 10 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]_n ( 11 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)N(Me)CH₂Ph}]_n ( 12 ) and [(S)‐Me₂Ga{μ‐OCH₂(C₄H₇NHCH₂Ph)}]_n ( 13 ) result from the equimolar reactions of GaMe₃ with the corresponding alcohols. The new compounds were characterized by elemental analyses, ¹H‐, ¹³C‐ and ²⁷Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction.     

Synthesis and characterization of organic-inorganic hybrid compounds with a pillared layer structure: Ga2(4,4′-bpy)(XO4)2 (X=P, As)

Two organic-inorganic hybrid compounds, Ga₂(4,4′-bpy)(PO₄)₂, 1, and Ga₂(4,4′-bpy)(AsO₄)₂, 2, have been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. The two compounds are isostructural and crystallize in the triclinic space group (No. 2) with a=4.9723(9) Å, b=5.770(1) Å, c=11.812(2) Å, α=78.268(3)°, β=89.159(3)° γ=88.344(3)°, V=331.7(2) Å³, Z=1, and R1=0.0377 for 1, and a=5.1111(7) Å, b=5.9327(8) Å, c=11.788(2) Å, α=79.497(2)°, β=88.870(2)°, γ=88.784(2)°, V=351.3(2) Å³, and R1=0.0264 for 2. The structure consists of neutral sheets of GaXO₄ (X=P or As) which are pillared through 4,4′-bipyridine ligands. Each oxide layer, which is formed only by four-membered rings, is constructed from corner-sharing GaO₄N trigonal bipyramids and XO₄ tetrahedra. The title compounds are two of the few examples in which the gallium atoms are exclusively five-coordinate.     

Donorstabilisierte Galliumdihalogenide Ga2X4·2D (X = Cl,Br; D = Donormolekül): Ein experimenteller Beitrag zu den Variationsmöglichkeiten der Ga‐Ga‐Einfachbindung

Donor‐stabilized Galliumdihalides Ga₂X₄·2D (X = Cl, Br; D = Donor): An Experimental Contribution on the Variation of the Gallium‐Gallium Single Bond During the disproportionation of metastable GaX‐solutions (X= Cl, Br) donor‐stabilized galliumdihalides are formed as oxidized products. According to X‐ray structure analyses they all exhibit dimeric entities DX₂Ga‐GAX₂D (D= THF, NHEt2, NEt3, 4‐^tButylpyridin or Br^‐), which means these compounds are isoelectronic with ethane and could schematically be regarded as representatives of catenulate or alkane‐like gallium subhalides: Ga_n(X, D)_2n+2. The gallium‐gallium bond in these compounds is shorter than in the organometallic compounds such as R₂Ga‐GaR₂. The comparison of the bonding situation in the galliumdihalides, particularly of the gallium‐gallium bond, shows clearly the influence by donor molecules as well as by halogen ligands.     

Synthese und Kristallstrukturen der Phosphaniminato-Komplexe [MCl2(NPPh3)]2 mit M = Al und Ga, [SbCl2(NPMe3)(DMF)]2 sowie des Phosphanimin-Komplexes [Ph3PNH · BF3] · THF

Syntheses and Crystal Structures of the Phosphorane Iminato Complexes [MCl₂(NPPh₃)]₂ with M = Al and Ga, [SbCl₂(NPMe₃)(DMF)]₂, and of the Phosphorane Imine Complex [Ph₃PNH · BF₃] · THF The phosphorane iminato complexes [MCl₂(NPPh₃)]₂ with M = Al and Ga and [SbCl₂(NPMe₃)(DMF)]₂ are formed as colourless crystals by reactions of the anhydrous trichlorides MCl₃ (M = Al, Ga, Sb) with the corresponding silylated phosphorane imines Me₃SiNPR₃ in acetonitrile and in dimethyl formamide, respectively. The phosphorane imine derivative [Ph₃PNH · BF₃] · THF is formed from Me₃SiNPPh₃ and boron trifluoride etherate in boiling tetrahydrofuran. The compounds are characterized by their i. r. spectra and by crystal structure analyses. [AlCl₂(NPPh₃)]₂ : Space group P1 , Z = 1, structure solution with 1 585 observed unique reflections, R = 0.061. Lattice dimensions at ?70°C: a = 917.6, b = 1 053.5, c = 1 145.2 pm, α = 111.72°, β = 100.80°, γ = 109.95°. [GaCl₂(NPPh₃)]₂ : Space group P1 , Z = 1, structure solution with 2 586 observed unique reflections, R = 0.066. Lattice dimensions at ?70°C: a = 917.5, b = 1 058.3, c = 1 153.7 pm, α = 105.52°, β = 107.75°, γ = 109.88°. In both compounds the metal atoms are linked to planar M₂N₂ four-membered rings via the N-atoms of the phosphorane iminato groups. [SbCl₂(NPMe₃)(DMF)]₂ : Space group P2₁/n, Z = 4, structure solution with 3 805 observed unique reflections, R = 0.038. Lattice dimensions at ?70°C: a = 1 913.0, b = 726.8, c = 2 040.7 pm, β = 113.62°. The unit cell contains two symmetry independent dimeric molecules, in which the antimony atoms are centrosymmetricly μ₂ linked via the N-atoms of the phosphorane iminato groups. Along with the oxygen atom of the dimethyl formamide molecule the Sb atoms achieve a ψ-octahedral environment. [Ph₃PNH · BF₃] · THF : Space group C2/c, Z = 8, structure solution with 2 048 observed unique reflections, R = 0.058. Lattice dimensions at ?70°C: a = 2 460.4, b = 869.2, c = 1 978.0 pm, β = 116.35°.