Indium-catalyzed Barbier allylation reaction

Barbier allylation reaction of carbonyl compounds with allyl bromide was investigated using a catalytic amount of indium (0), indium (I) or indium (III) salts in the presence of a reducer and chlorotrimethylsilane (TMSCl). The Mn/TMSCl couple turned out to be the most efficient system to regenerate active indium in the allylation reaction of various carbonyl compounds including α- and β-oxygenated aldehydes.     

Synthesis of water-tolerant indium homoenolate in aqueous media and its application in the synthesis of 1,4-dicarbonyl compounds via palladium-catalyzed coupling with acid chloride

The first water-tolerant, ketone-type indium homoenolate was synthesized via the oxidative addition of In/InCl(3) to enones. The reaction proceeds exclusively in aqueous media. Both indium and indium(III) chloride are necessary for the smooth conversion of the reaction. Similar results were obtained when InCl or InCl(2) was used in place of In/InCl(3). The synthetic utility of the indium homoenolate was demonstrated through the synthesis of 1,4-dicarbonyl compounds via palladium-catalyzed coupling of indium homoenolate with acid chloride.     

Determination of indium and tin by activation analysis using replacement substoichiometry

A new method for the determination of indium by activation analysis has been developed. It is based on the replacement of indium from indium dithizonate (in carbon tetrachloride) by a substoichiometric amount of aqueous mercury(II) solution. Preliminary steps are the extraction of indium from alkaline cyanide solution with an excess of dithizone solution and washing the extract with buffer solution. The time necessary for the separation is 10-20 min. With this method indium can be determined by using either short ((116m)In, t(1 2 ) = 54 min) or long-lived radioisotopes ((114m)In, t(1 2 = 50 d). As by the reaction (112)Sn (n, gamma)) (113)Sn (119d) --> (113)In (104 min), indium-113m is formed, which has a different gamma-spectrum from that of indium-114m, the determination of both indium and tin is possible. The proposed method has been applied to the determination of indium and tin in granite and gallium.     

Hydrogen adsorption on the indium-rich indium phosphide (001) surface: a novel way to produce bridging In-H-In bonds

The indium phosphide (001) surface provides a unique chemical environment for studying the reactivity of hydrogen toward the electron-deficient group IIIA element, indium. Hydrogen adsorption on the In-rich delta(2 x 4) reconstruction produced a neutral, covalently bound bridging indium hydride. Using vibrational spectroscopy and ab initio cluster calculations, two types of bridging hydrides were identified, a (mu-H)In(2) and a (mu-H)(2)In(3) "butterfly-like" structure. These structures were formed owing to the large thermodynamic driving force for adsorption of H atoms on solid-state indium dimers.     

Synthesis of indium nanoparticles: digestive ripening under mild conditions

Here we report the synthesis of monodispersed indium nanoparticles by evaporation/condensation of indium shot using the solvated metal atom dispersion (SMAD) technique, followed by digestive ripening in low boiling point (BP 38 °C) methylene chloride and in a high boiling point (BP 110 °C) toluene solvent. The as-prepared SMAD indium nanoparticles are polydispersed with particle size ranging from 25 to 50 nm, but upon digestive ripening (heating of colloidal material at the boiling point of solvent in presence of excess surface active ligands) in methylene chloride, a remarkable reduction of particle size was achieved. In higher boiling solvent (toluene), where the indium nanoparticles at reflux temperature are probably melted, it does not allow the best result, and less monodispersity is achieved. We employed different surface active ligands (amine, phosphine, and mixed ligands) to passivate these indium nanoparticles. The temporal evolution of the surface plasmon of indium nanoparticles was monitored by in situ UV-vis spectroscopy, and particles were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The merits of this synthesis procedure are the use of bulk indium as starting material, tuning the particle size in low boiling point solvent, particle size adjustment with the choice of ligand, and a possible scale up.     

Indium(III) acetate-catalyzed intermolecular radical addition of organic iodides to electron-deficient alkenes

In the presence of phenylsilane and a catalytic amount of indium(III) acetate, organic iodides added to electron-deficient alkenes in ethanol at room temperature. Both simple and functionalized organic iodides were applicable to this reaction. A plausible reaction mechanism involves the formation of indium hydride species by hydride transfer from silicon to indium and an indium hydride-mediated radical chain process.     

Nuclear chemistry of indium and related compounds

The activation of indium by gamma-ray source through absorption of photons of resonance energy and the threshold energy (appearance energy) determination in indium compounds as well as some results of hot atom chemistry studies of indium compounds and of implantation with indium ions are described.     

Role of humidity on indium and tin migration in organic photovoltaic devices

The stability of a common interface used in organic photovoltaic cells, between the transparent electrode of Indium Tin Oxide (ITO) and a buffer layer of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) is strongly influenced by the presence of humidity during processing, leading to significant migration of indium and tin species into the PEDOT:PSS layer. The interface was studied using neutral impact collision ion scattering spectroscopy (NICISS) and X-ray photoelectron spectroscopy (XPS), to determine migration of indium and tin into the polymer layer. It was found that the migration starts almost instantly after spin coating of the aqueous PEDOT:PSS solution and it reaches a saturation level within twenty four hours. The indium and tin were found always uniformly distributed over the sampling depth of almost one-third of the thickness of the PEDOT:PSS layer. Exposure to humidity following annealing resulted in the highest concentration (1.8 × 10(-3) mol cm(-3)) of indium or tin species, corresponding to about one indium or tin moiety per 4.7 monomer units in the PEDOT:PSS. The maximum bulk concentration of indium is about two orders of magnitude higher after exposure to humid conditions compared to vacuum dried conditions. XPS measurements confirm the presence of both indium and tin in the PEDOT:PSS and the formation of salts with the metal ions as cations.     

Electron beam induced reactions of oxygen on the InP(110) surface

An electron beam bombardment of the InP(110) cleaved surface causes a decomposition, an oxidation and a carbon contamination of the irradiated area even in ultrahigh vacuum conditions. The formation of phosphorus oxide is obvious from visual inspection of the P LMM Auger spectra. The indium MNN Auger line shape is rather insensitive to the chemical environment, hence, the determination of the indium bonding state is more difficult. We show the pattern recognition evaluating methods are able to distinguish mettalic indium form from indium bonded to phosphorus and indium bonded to oxygen.     

Polarographic determination of indium(III) after salting-out extraction of the bromide complex into acetonitrile

A simple and sensitive method has been developed for the polarographic determination of indium(III) after solvent extraction into acetonitrile, salted-out from aqueous solution with sodium bromide. The extracted indium(III)-bromide complex gives a well-defined d.c. wave with E(1 2 ) = -0.69 V vs. SCE. The wave-height is directly proportional to the concentration of indium(III) from 1.6 x 10(-6) to 3.0 x 10(-4)M with respect to the original aqueous solution. In the a.c. polarographic method, a linear calibration curve is obtained for indium(III) over the concentration range from 1.6 x 10(-6) to 1.5 x 10(-5)M, and interference from most foreign ions can be eliminated. In particular, 10.0 mg of Fe(III) and 2.5 mg of Tl(III) are tolerated when 1.0 g of ascorbic acid is added. The lower limit of determination is 8 x 10(-8)M indium(III) by the square-wave polarographic method.     

Control of diastereoselectivity in the crotylation and cinnamylation of aldehydes by the selection of ligands on allylic indium reagents

Diastereoselective couplings of salicylaldehyde, anisaldehyde and 2-pyridylaldehyde with crotyl- and cinnamylindium reagents were studied. The syl/anti selectivity was found to depend largely on the ligands on the indium atom of the allylic indium reagents. A syn-selective cinnamylation of salicylaldehyde was realized by the combination of cinnamyl acetate and indium(I) iodide, whereas an anti-selective coupling with salicylaldehyde was achieved by the indium trichloride/aluminium-mediated cinnamylation.     

Determination of indium by graphite furnace atomic absorption spectrometry after coprecipitation with chitosan.

A sensitive and simple method for the determination of trace amounts of indium in water samples by graphite furnace atomic absorption spectrometry (GFAAS) after coprecipitation with chitosan was investigated. Indium was quantitatively preconcentrated from water samples by coprecipitation with chitosan at pH 7.0-9.0. The coprecipitant was easily dissolved with acetic acid, and indium in the resulting solution was determined by GFAAS. The addition of lanthanum as a chemical modifier was more effective for the atomic absorbance of indium. The detection limit (S/N > or = 3) for indium was 0.04 microg dm(-3), and the relative standard deviations (n = 5) were 3.5-4.5% at 1.0 microg/100 cm3. The results obtained in this study indicate that the proposed method can be successfully applied to the determination of trace indium in water samples.     

Study of the binding of 114mIn radiotracer to human serum components by ultrafiltration and chromatography

The chemical speciation of indium in serum was studied. Ultrafiltration was used to investigate the influence of several buffer systems on the binding characteristics of indium in serum and to study the association of indium with transferrin and albumin. This was performed by means of batch incubation experiments with a 114mIn tracer. Different buffer systems were investigated. A series of bicarbonate, Tris:HCl and HEPES buffers were found to fit for this purpose. Phosphate buffer was not suitable, as it is capable of disrupting the binding between indium and transferrin. Batch ultrafiltration experiments with 114mIn incubated solutions of transferrin and albumin showed that both proteins are capable of binding indium to a high degree. Three chromatographic techniques (SEC, AEC, AC) were used to study the different chemically active species of indium in serum. It is concluded that next to transferrin, albumin is also responsible for the binding and transport of indium in serum.     

Direct spectrophotometric determination of indium in tin

Indium is separated from tin by an anion-exchange process in 0.5 M hydrochloric acid solution. Subsequently, the indium is extracted into 1,2-dichlorobenzene as its complex with 5,7-dichloro-8-quinolinol. The complex forms and extracts quantitatively in the pH range 3–7. The yellow, organic phase is measured spectrophotometrically at 415 mμ; ; its absorbancy is directly proportional to the indium content of the aqueous phase up to a total of 1.5 mg of indium per 50 ml. This procedure quantitatively separates the two metals, allows one to determine the indium content of indium(<5%)-tin alloys with a relative error less than 0.7%, and considerably reduces color fading errors inherent in some previously reported spectrophotometric methods for indium.     

Bone marrow scintigraphy with 111In-chloride--a clinical value for the hematological diseases

Bone marrow scintigraphy with indium chloride (111In) was performed in fifty-one patients with the hematological diseases. The results of the investigation were that 1. in all patients, as well as in patients with aplastic anemia, no correlation was there between the degree of the indium chloride accumulation and peripheral blood counts, 2. in patients with aplastic anemia and pure red cell aplasia (PRCA) a tendency to reduction in uptake of indium chloride in bone marrow, 3. in patients with these two good correlation between the degree of indium chloride accumulation and histology of the erythroid bone marrow, but in patients with chronic myelocytic leukemia (CML) and atypical leukemia no correlation between the two, so it seemed unlikely that indium chloride should reflect the effective production of erythrocytes, 4. four patients with leukemia were studied with indium chloride bone marrow imaging two times to evaluate their responses to chemotherapy, and peripheral expansion was no change or reduced in two patients with acute myelocytic leukemia (AML) and one patient with acute lymphocytic leukemia (ALL) who obtained complete remission, but on the other hand, it enlarged in one patient with acute myelocytic leukemia who obtained partial remission, and 5. in two patients with chronic myelocytic leukemia it enlarged up to the ankle joints, which was considerably specific.     

3,5,7,4'-Tetrahydroxyflavone (kaempferol) as a chromogenic reagent for gallium and indium

3,5,7,4'-Tetrahydroxyflavone (kaempferol) forms yellow chelates with indium and gallium. Based on this reaction, a sensitive spectrophotometric method for the determination of gallium and indium alone and in presence of other metals and alloys has been developed. Beer's law is obeyed up to 2.8 and 1.44 ppm for indium and gallium respectively.     

Indium(I) trifluoromethanesulfonate and other soluble salts for univalent indium chemistry

Herein we report the synthesis, structure and preliminary reactivity studies of a series of unusually soluble indium(i) salts that are improved alternatives to indium(i) halide reagents.     

Subtoichiometric determination of indium and tin by radioactivation analysis

A method of radioactivation analysis has been developed for the determination of indium and tin. It is based on substoichiometric extraction of indium diethyldithiocarbamate into carbon tetrachloride from a slightly ammoniacal solution in the presence of potassium cyanide. With this method, indium can be determined via^116m In (T=54 min) and tin via^113m In (T=104 min) which is formed by the reaction¹¹²Sn(n, ψ)¹¹³Sn. The method has been applied to the determination of indium in metallic zinc and of tin in tin-doped gallium arsenide, and 0.4 ppb of indium was analyzed in a zinc sample.     

Indium phthalocyanines with different axial ligands: a study of the influence of the structure on the photophysics and optical limiting properties

The photophysical properties of four axially substituted indium phthalocyanines, namely, 2,(3)-tetra- tert-butyl-phthalocyaninato indium chloride ( 1), 2,(3)-tetra-[(3,5-di- tert-butyl)-phenyloxy]-phthalocyaninato indium bromide ( 2), 2,(3)-tetra-[(3,5-di- tert-butyl)-phenyloxy]-phthalocyaninato indium iodide ( 3), and 2,3-octa-[(2-hexyl)-ethyloxy]-phthalocyaninato indium trifluoroacetate ( 4), have been investigated, and their optical limiting properties with nanosecond light pulses were evaluated. All complexes behave as reverse saturable absorbers in the range of 400-625 nm due to a triplet-triplet excited-state transition. Excited-state absorption cross sections and triplet state lifetimes are not significantly affected by the nature of the axial ligand. On the other hand, remarkable differences in the variation of nonlinear transmittance are observed for 1- 4 due to significantly different intersystem crossing rates. Heavier axial ligands in phthalocyanines 2 and 3 produce the largest variations of nonlinear transmission (heavy-atom effect). Complex 1 in polystyrene matrix shows reversible nonlinear absorption when incident fluence does not exceed 0.025 J cm (-2).     

Spectrophotometric determination of traces of gallium and indium with 1-(2-pyridylazo)-2-naphthol

1-(2-Pyridylazo)-2-naphthol (PAN) reacts with either gallium or indium at pH 5–6 giving a red complex in an aqueous medium in the presence of N.N-dimethyl-formamide. The maximum absorption of both PAN complexes of gallium and indium in an aqueous solution is at 545 mμ. The gallium-PAN complex shows a characteristic enhancement of color by addition of small amounts of ethers. Based on this selective enhancement reaction, gallium can be determined in the presence of other metals without separation. The results of determining gallium and indium in the presence of each other are reported. Both gallium and indium form M₂(PAN)₃; but in the presence of certain organic solvents, a different gallium complex, Ga(PAN)₅, and the same indium complex, In₂(PAN)₃, are formed. The reaction of PAN with cadmium can be masked by iodide; an example of determining indium in the presence of cadmium is given. The PAN method has a sensitivity of 0.003 μg/cm² for gallium and 0.005μg/cm² for indium and an absorptivity of 24,900 for the Ga-PAN complex and of 24,500 for the In-PAN complex, respectively. The methods have been successfully applied to the determination of both gallium and indium in germanium thin films.