Rhenium chelate complexes with maltolate or kojate

Novel rhenium complexes containing the maltolate (mal) or kojate (koj) anions as chelating ligands have been synthesized: [ReOCl(mal)₂] (1), [ReOCl₂(mal)(PPh₃)] (2), [ReOBr₂(mal)(PPh₃)] (3), [ReOCl₂(koj)(PPh₃)] (4) and [ReOBr₂(koj)(PPh₃)] (5). The products have been characterized by FTIR, ¹H, ¹³C, and ³¹P NMR spectroscopies and elemental analysis. The crystal and molecular structures of all complexes were determined. Complex 1 crystallizes monoclinic, space group C2/c, Z = 8. It contains two O,O′-bidentate maltolate ligands and one chloro ligand at the (ReO)³⁺ unit, so that a distorted octahedral geometry is adopted by the six-coordinated rhenium(V) center. The chloro ligand occupies a cis position to the oxo ligand. Complexes 2 and 3 are isostructural and crystallize orthorhombic, space group Pbca and Z = 8. The isostructural complexes 4 and 5 crystallize monoclinic, space group P2₁/n and Z = 4. In complexes 2–5, the (ReO)³⁺ unit is coordinated by a monoanionic O,O-bidentate unit of the maltolate (2 and 3) or kojate (4 and 5) ligand, one triphenylphosphine and two halogeno ligands (Cl in 2 and 4; Br in 3 and 5), with the rhenium(V) center in a distorted octahedral environment. The halide ligands are in cis positions to each other.     

Interaction of gallium, indium, thallium, germanium, tin, and lead with boron

Summary Investigations of the interaction of boron with gallium, indium, thallium, germanium, tin, and lead with boron showed that these elements do not form chemical compounds or solid solutions with boron.The absence of any interaction between these elements and boron is explained in the light of a discussion of the electronic structure and energy characteristics of the valence electrons of metals of the IIIB and IVB subgroups of the periodic system.Translated from Zhurnal Strukturnoi Khimii, Vol. 1, No. 4, pp. 458–463, November–December, 1960     

铕(III)离子与人血清脱铁转铁蛋白结合的紫外差光谱研究

在pH7.4,温度为25℃的条件下,用紫外吸收差光谱进行了Eu^3^+对人血清脱铁转铁蛋白的滴定。结果表明Eu^3^+与人血清脱铁转铁蛋白结合后其差光谱在245nm和296nm处出现吸收峰,在245nm处,Eu^3^+-脱铁转铁蛋白配合物的摩尔吸光系数是(2.2±0.1)×10^4cm^-^1.mol^-^1.dm^3,Eu^3^+可占据脱铁转铁蛋白的2个金属离子结合部位,Eu^3^+优先占据脱铁转铁蛋白的C端结合部位,条件平衡常数是logK~C=8.42±0.12,logK~N=6.03±0.42。Eu^3^+与R~E^3^+(R~E=Nd,Sm,Gd和Tb)间的线性自由能关系表明,稀土离子占据脱铁转铁蛋白的C端结合部位时受离子大小的影响。     

Extraction of gallium with tetraphenylarsonium chloride

Summary Gallium is completely extracted with tetraphenylarsonium chloride from hydrochloric acid medium. The extraction behavior was studied by determining gallium with complexometric titration using gallocyanine indicator, spectrophotometrically with rhodamine B, and also with gallium-72 tracer. Complete extraction is observed from 2.5M hydrochloric acid; the extractable species is GaCl₄ ^–, (C₆H₅)₄As⁺. In the presence of lithium chloride (total chloride ion concentration 2.5M) complete extraction occurs at hydrochloric acid concentrations 0.25M. The following ions do not interfere: aluminum, thallium, zinc, cadmium, mercury, cobalt, nickel, permanganate, molybdate, tungstate, tin, phosphate and fluoride.

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Zusammenfassung Gallium läßt sich aus salzsaurem Medium vollständig mit Tetraphenyl-arsoniumchlorid extrahieren. Das Extraktionsverhalten wurde durch Bestimmung des Galliums komplexometrisch mit Gallocyanin als Indikator, spektrophotometrisch mit Rhodamin B und radiometrisch mit⁷²Ga untersucht. Vollständige Extraktion erhält man, wenn die Salzsäure mindestens 2,5-m ist, wobei (C₆H₅)₄As[GaCl₄] extrahiert wird. In Gegenwart von Lithiumchlorid genügt eine geringere Salzsäurekonzentration, wenn [Cl^–]2,5. Folgende Ionen stören nicht: Al³⁺, Th⁺, Zn²⁺, Cd²⁺, Hg²⁺, Co²⁺, Ni²⁺, MnO₄ ^–, MoO₄ ^2–, WO₄ ^2–, Sn²⁺, PO₄ ^3– und F^–.

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This work was partially supported by the U. S. Atomic Energy Commission, Contract No. At (30-1)-3417.     

Photometric determination of gallium with rhodamine b

Gallium is extractable as rhodamine B chlorogallate with benzene from 6M hydrochloric acid, and can be determined absorptiometrically or fluorimetrically in the extract. The interference of iron(III) is avoided by first separating gallium by extraction with isopropyl ether from hydrochloric acid solution containing titanous chloride. Traces of gallium can be determined in the presence of aluminium, indium, zinc, antimony, thallium, tungsten and other elements.     

Synthesis and characterization of nickel(II) maltolate complexes containing ancillary bisphosphine ligands

Cationic nickel(II) complexes containing chelating O,O′-donor maltolate or ethyl maltolate ligands in conjunction with bidentate bisphosphine ligands Ph₂P(CH₂) _n PPh₂ were prepared by a one-pot reaction starting from nickel(II) acetate, bisphosphine, maltol (or ethyl maltol), and trimethylamine, and isolated as their tetraphenylborate salts. An X-ray structure determination of [Ni(maltolate)(Ph₂PCH₂CH₂PPh₂)]BPh₄ shows that the maltolate ligand binds asymmetrically to the (slightly distorted) square-planar nickel(II) center. The simplicity of the synthetic method was extended to the synthesis of the known platinum(II) maltolate complex [Pt(maltolate)(PPh₃)₂]BPh₄ which was obtained in high purity.     

Determination of aluminium and gallium: Chelate formation of trivalent aluminium and gallium with eriochrome cyanine RC

Summary ECRC forms violet coloured chelates with aluminium(III) and gallium(III) with _max 540 nm and 550 nm respectively at p_H 4.5 and 3.5. The metal ligand ratio in both the cases has been found to be 11. The chelates of aluminium and gallium are stable between p_H 3.5 to 5.5 and p_H 2.7 to 6.0 respectively. The apparent stability constants are 10^4.9 (p_H 4.5) and 10^4.8 (p_H 3.8) respectively for the aluminium and gallium chelates at 25°. The range of concentration for adherence toBeer's law, the effective range of photometric determination and the molar absorptivities are 0.27 to 0.97 p. p. m.; 0.18 to 0.97 p. p. m. and 3.20 · 10⁴ for aluminium, and 0.093 to 2.52 p. p. m.; 0.46 to 2.52 p. p. m. and 2.20 ·10⁴ for gallium respectively.

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Zusammenfassung Eryochromcyanin RC bildet mit Al(III) und Ga(III) violett gefärbte Chelate, die bei p_H 4,5 bzw. 3,5 Absorptionsmaxima bei 540 bzw. 550 run haben. In beiden Fällen ist das Verhältnis Metall: Ligand=11. Die Chelate sind zwischen p_H 3,5 und 5,5 bzw. zwischen p_H 2,7 und 6,0 stabil. Die entsprechenden Konstanten lauten 10^4,9 (p_H 4,5) bzw. 10^4,8 (p_H 3,8) bei 25°. Bei Al liegt der Gültigkeitsbereich für das Beersche Gesetz zwischen 0,27 und 0,97 ppm; für die photometrische Bestimmung zwischen 0,18 und 0,97 ppm. Die molare Extinktion beträgt 3,20 · 10⁴. Die entsprechenden Werte für Gallium lauten: 0,093 bis 2,52 ppm; 0,46 bis 2,52 ppm und 2,20 · 10⁴.

     

1-苯基-3-甲基-4-苯甲酰吡唑啉酮-5萃取镓的研究

首次报道了1-苯基-3-甲基-4-苯甲酰吡唑啉酮-5(HPMBP)萃取镓的热力学和动力学, 指出在体系中形成Ga(PMBP)3(H2O)2萃合物, 配体PMBP既有一次溶剂化作用, 又有二次溶剂化作用, 并得到红外光谱和核磁共振谱的证实。镓的萃取过程为水相化学反应控制, 决速步骤为一次溶剂化过程: Ga^3^++HPMBP→Ga(PMBP)^2^++H^+。添加剂三辛基氧化膦(TOPO)不影响HPMBP萃取镓的分配比, 但降低了HPMBP萃取镓的正向速率, 表明动力学抑萃作用与热力学抑萃作用无对应关系。     

Disulfidation of alkynes and alkenes with gallium trichloride

[reaction: see text] Treatment of diphenyl disulfide and terminal alkynes with gallium trichloride afforded (E)-1,2-diphenylthio-1-alkenes selectively (E/Z > 20/1). Alkenes also underwent this reaction to form trans adducts.     

High-performance liquid chromatographic separation of human apotransferrin and monoferric and diferric transferrins

A simple method for the chromatographic separation of the different molecular forms of human transferrin according to their respective iron contents is described. The appropriate conditions were developed with a Mono-S cation-exchange column.     

控制电位氟-镓配位滴定法测定镓

以氟离子溶液作滴定剂,氟离子选择性电极作指示电极,利用氟-镓之间的配位反应及控制电位滴定法,对镓的测定进行了研究.控制溶液的pH约为4.2,实验温度为298 K,离子强度调节剂(NaNO3)的浓度为0.1 mol/L.对溶液控制的pH,氟离子的酸效应和镓离子的羟基配位效应对测定结果的影响,共存的Cu2 ,Zn2 ,Ni2 及Co2 等离子的干扰进行了讨论.     

Ferrocenophanes with gallium and silicon as alternating bridges

[1.1]Ferrocenophanes with gallium and silicon in bridging positions have been prepared in yields of 29 and 41%, respectively. From the same reactions, polymer-containing fractions were isolated (31% in each case) and shown to be comprised of linear and cyclic species with up to 16 ferrocene units (MALDI-TOF analysis).     

Complexometric determination of gallium with calcein blue as indicator

A metalfluorechromic indicator, Calcein Blue, has been used for the back-titration of milligram amounts of EDTA in presence of gallium complexes. The indicator was used in conjunction with an ultraviolet titration assembly equipped with a cadmium sulphide detector cell and a microammeter for enhanced end-point detection. The result is a convenient and rapid method with an accuracy approaching 0.1% and a relative standard deviation of about 0.4% for 10 mg of gallium.     

Oligonuclear gallium nitrogen cage compounds: molecular intermediates on the way from gallium hydrazides to gallium nitride

Gallium hydrazides are potentially applicable as facile starting compounds for the generation of GaN by thermolysis. The decomposition pathways are, however, complicated and depend strongly on the substituents attached to the gallium atoms and the hydrazido groups. This paper describes some systematic investigations into the thermolysis of the gallium hydrazine adduct Bu(t)(3)Ga←NH(2)-NHMe (1a) and the dimeric gallium hydrazides [R(2)Ga(N(2)H(2)R')](2) (2b, R = Bu(t), R' = Bu(t); 2c, R = Pr(i), R' = Ph; 2d, R = Me, R' = Bu(t)) which have four- or five-membered heterocycles in their molecular cores. Heating of the adduct 1a to 170 °C gave the heterocyclic compound Bu(t)(2)Ga(μ-NH(2))[μ-N(Me)-N(=CH(2))]GaBu(t)(2) (3) by cleavage of N-N bonds and rearrangement. 3 was further converted at 400 °C into the tetrameric gallium cyanide (Bu(t)(2)GaCN)(4) (4). The thermolysis of the hydrazide (Bu(t)(2)Ga)(2)(NH-NHBu(t))(2) (2b) at temperatures between 270 and 420 °C resulted in cleavage of all N-N bonds and the formation of an octanuclear gallium imide, (Bu(t)GaNH)(8) (6). The trimeric dialkylgallium amide (Bu(t)(2)GaNH(2))(3) (5) was isolated as an intermediate. Thermolysis of the hydrazides (Pr(i)(2)Ga)(2)(NH-NHPh)(NH(2)-NPh) (2c) and (Me(2)Ga)(2)(NH-NHBu(t))(2) (2d) proceeded in contrast with retention of the N-N bonds and afforded a variety of novel gallium hydrazido cage compounds with four gallium atoms and up to four hydrazido groups in a single molecule: (Pr(i)Ga)(4)(NH-NPh)(3)NH (7), (MeGa)(4)(NH-NBu(t))(4) (8), (MeGa)(4)(NH-NBu(t))(3)NBu(t) (9), and (MeGa)(4)(NHNBu(t))(3)NH (10). Partial hydrolysis gave reproducibly the unique octanuclear mixed hydrazido oxo compound (MeGa)(8)(NHNBu(t))(4)O(4) (11).     

Spectroscopy of laser-excited indium,gallium and indium–gallium systems

The spectroscopy of dense Ga, In and In–Ga vapours is studied via resonant pulsed laser excitation at 403.4 nm (Ga) and 410.3 nm (In). Besides some known atomic Rydberg levels emission, satellite wings on the blue side of the fundamental transitions show up both in the homonuclear and heteronuclear vapours. They are due to the presence of excited homonuclear dimers that form in the collision between excited and ground-state atoms. The formation of heteronuclear dimers is inferred by the time-resolved analysis of some atomic fluorescences.