Properties and analytical applications of the heteropolymolybdates of phosphorus, arsenic, silicon and germanium-III Examination of two- and three-component systems without separation

By taking advantage of the possible variations in acid and molybdenum concentration, wavelength of measurement, alpha- and beta-modifications, and media, P, As, Si and Ge can be determined spectrophotometrically as the heteropolymolybdates without separation. Rapid procedures are proposed for the analysis of two- and three-component mixtures of these elements.     

Separation of radioarsenic from irradiated germanium oxide targets for the production of <Superscript>71</Superscript>As and <Superscript>72</Superscript>As

A method for the separation of no-carrier-added arsenic radionuclides from the bulk amount of proton-irradiated GeO₂ targets as well as from coproduced radiogallium was developed. The radionuclides ⁶⁹Ge and ⁶⁷Ga produced during irradiation of GeO₂ were used as tracers for Ge and Ga in the experiments. After dissolution of the target the ratio of As(III) to As(V) was determined via thin layer chromatography (TLC). The extraction of radioarsenic by different organic solvents from acid solutions containing alkali iodide was studied and optimized. The influence of the concentration of various acids (HCl, HClO₄, HNO₃, HBr, H₂SO₄) as well as of KI was studied using cyclohexane. The optimum separation of radioarsenic was achieved using cyclohexane with 4.75 M HCl and 0.5 M KI and its back-extraction with a 0.1% H₂O₂ solution. The separation leads to high purity radioarsenic containing no radiogallium and <0.001% [⁶⁹Ge]Ge. The overall radiochemical yield is 93 ± 3%. The practical application of the optimized procedure in the production of ⁷¹As and ⁷²As is demonstrated and batch yields achieved were in the range of 75–84% of the theoretical values.     

Elucidating the Germanium Distribution in ITQ-13 Zeolites by Density Functional Theory**

ITQ-13 is a medium-pore zeolite that can be prepared in all-silica form and as silicogermanate with Si/Ge ratios as low as 3. Usually synthesised in the presence of fluoride, ITQ-13 is among the very few systems containing fluoride anions in two distinct cage types, cube-like d4r units and [4 ⋅ 5⁶] cages. Here, dispersion-corrected density functional theory (DFT) calculations are used to investigate the energetically most favourable Ge distributions for Si/Ge ratios between 55 and 6. The calculations show Ge atoms are incorporated at both the corners of d4r cages and at the basal plane of the [4 ⋅ 5⁶] cages, in accordance with ¹⁹F NMR spectroscopy. Two Ge atoms at adjacent corners of [4 ⋅ 5⁶] cages are stable at the highest Ge content considered (Si/Ge=6). Such a local environment has not yet been considered in the experimental literature. A calculation of the corresponding ¹⁹F NMR resonance points to overlap with other resonances, which might preclude its clear identification. Additional calculations investigate the variation of the dynamic behaviour of the fluoride anions as a function of the local environment as well as the selective defluorination of the [4 ⋅ 5⁶] cages.     

Tris(trichlorosilyl)tetrelide Anions and a Comparative Study of Their Donor Qualities

Trichlorosilylated tetrelides [(Cl₃Si)₃E]⁻ have been prepared by adding 1 equiv of a soluble Cl⁻ salt to (Cl₃Si)₄Si (E=Si) or 4 Si₂Cl₆/GeCl₄ (E=Ge). To assess their donor qualities, the anions [(Cl₃Si)₃E]⁻ (E=C, Si, Ge) have been treated with BCl₃, AlCl₃, and GaCl₃. Both BCl₃ and GaCl₃ give 1:1 adducts with the anionic centers. AlCl₃ leads to Cl⁻ abstraction from [(Cl₃Si)₃E]⁻ with formation of (Cl₃Si)₄E (E=Si or Ge). (Cl₃Si)₄Ge is cleanly converted to the perhydrogenated (H₃Si)₄Ge by use of Li[AlH₄]. Another case of Cl⁻ abstraction was observed for [(Cl₃Si)₃Ge ⋅ GaCl₃]⁻, which reacts with GaCl₃ to afford the neutral dimer [(Cl₃Si)₃Ge−GaCl₂]₂.     

Ab initio Study on Formation Mechanism of Spiro-Si-Heterocyclic Ring Compound Involving Ge from H2Ge=Si: and Formaldehyde

H₂Ge=Si: and its derivatives (X₂Ge=Si:, X=H, Me, F, Cl, Br, Ph, Ar,…) are new species. Its cycloaddition reactions are new area for the study of silylene chemistry. The cycloaddition reaction mechanism of singlet H₂Ge=Si: and formaldehyde has been investigated with the MP2/aug-cc-pVDZ method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rule is that two reactants firstly form a four-membered Ge-heterocyclic ring silylene through the [2+2] cycloaddition reaction. Because of the 3p unoccupied orbital of Si: atom in the four-membered Ge-heterocyclic ring silylene and the π orbital of formaldehyde forming a π→p donor-acceptor bond, the four-membered Ge-heterocyclic ring silylene further combines with formaldehyde to form an intermediate. Because the Si: atom in the intermediate undergoes sp³ hybridization after transition state, then the intermediate isomerizes to a spiro-Si-heterocyclic ring compound involving Ge via a transition state. The result indicates the laws of cycloaddition reaction between H₂Ge=Si: or its derivatives (X₂Ge=Si:, X=H, Me, F, Cl, Br, Ph, Ar,…) and asymmetric π-bonded compounds are significant for the synthesis of small-ring involving Si and Ge and spiro-Si-heterocyclic ring compounds involving Ge.     

Diamondoids approach to electronic,structural, and vibrational properties of GeSi superlattice nanocrystals: a first-principles study

Germanium silicide diamondoids are used to determine electronic, structural, and vibrational properties of GeSi superlattice nanocrystals and bulk as their building block limit. Density functional theory at the generalized gradient approximation level of Perdew, Burke, and Ernzerhof (PBE) with 6-31G(d) basis including polarization functions is used to investigate the electronic structure of these diamondoids. The investigated molecules and diamondoids range from GeSiH₆ to Ge₆₃Si₆₃H₉₂. The variation of the energy gap is shown from nearly 7 eV toward bulk value which is slightly higher than the average of Si and Ge energy gaps. Variations of bond lengths, tetrahedral, and dihedral angles as the number of atoms increases are shown taking into account the effect of shape fluctuations. Localized and delocalized electronic charge distribution and bonds for these molecules are discussed. Vibrational radial breathing mode (RBM) converges from its initial molecular value at 332 cm^?1 to its bulk limit at 0 cm^?1 (blue shift). Longitudinal optical-highest reduced mass mode (HRMM) converges from its initial molecular value 332 cm^?1 to experimental bulk limit at 420.7 cm^?1 (red shift). Hydrogen vibrational modes are nearly constant in their frequencies as the size of diamondoids increases in contrast with lower frequency Ge–Si vibrational modes. GeSi diamondoids can be identified from surface hydrogen vibrational modes fingerprint, while the size of these diamondoids can be identified from Ge–Si vibrational modes.     

SIMS for hydrogen quantification and structural analysis of amorphous silicon germanium compounds

Summary Hydrogen has been analysed quantitatively in a-Si_1–xGe_x:H alloys by SIMS with H variation from 1×10¹⁹ –1.3×10²² atoms/cm³ and x between 0 and 1. To quantify the absolute H concentration, SIMS measurements have been calibrated with nuclear reaction analysis, which exhibits excellent agreement with SIMS data for the total range of H and Ge variance. From abundances of the molecule ions SiH⁺ and GeH⁺ the fractions H bound to Si or Ge can be discerned and are in good accordance with quantification of SiH and GeH stretching modes in IR spectroscopic measurements. Preferential attachment of H to Si compared to Ge by a factor of 3.5 is determined for glow discharge a-SiGe:H samples; during annealing up to 900 K only small changes of this factor are observed.     

Phenylhydrosilocane as a source of silatranylium cations

Quantum chemical calculations were used for comparative analysis of the cations of the atrane structure [M(OCH₂CH₂)₃N]⁺ (M = Si or Ge) with classic three-coordinate cations R₃M⁺ of Group 14 elements. The possibility of nuclear chemical generation of atranylium cations in the condensed phase was experimentally demonstrated with silatranylium ions as examples.

     

Instrumental neutron activation analysis of an enriched 28Si single-crystal

The determination of the Avogadro constant plays a key role in the redefinition of the kilogram in terms of a fundamental constant. The present experiment makes use of a silicon single-crystal highly enriched in ²⁸Si that must have a total impurity mass fraction smaller than a few parts in 10⁹. To verify this requirement, we previously developed a relative analytical method based on neutron activation for the elemental characterization of a sample of the precursor natural silicon crystal WASO 04. The method is now extended to fifty-nine elements and applied to a monoisotopic ²⁸Si single-crystal that was grown to test the achievable enrichment. Since this crystal was likely contaminated, this measurement tested also the detection capabilities of the analysis. The results quantified contaminations by Ge, Ga, As, Tm, Lu, Ta, W and Ir and, for a number of the detectable elements, demonstrated that we can already reach the targeted 1 ng/g detection limit.     

Round‐robin test for the measurement of layer thickness of multilayer films by secondary ion mass spectrometry depth profiling

An international round‐robin test (RRT) was performed to investigate a method to determine the interface location and the layer thickness of multilayer films by secondary ion mass spectrometry (SIMS) depth profiling as a preliminary study to develop a new work item proposal in ISO/TC‐201. Two types of reference materials were used in this RRT. A SiGe alloy (Si_52.4Ge_47.6) reference film was used to determine the relative sensitivity factors of Si and Ge. A Si/Ge multilayer reference film was used to determine the relative sputtering rates of the Si and Ge layers. The layer thicknesses were measured from the interfaces determined by a 50 atomic percent definition. Seven laboratories from 5 countries participated in this international RRT. The RRT reference expanded uncertainties for Si and Ge layers in a Si/Ge multilayer with similar thicknesses as the reference film were 0.76 and 1.17 nm, respectively. However, those in a thinner Si/Ge multilayer film were slightly larger at 1.04 and 1.59 nm, respectively. Most of the thickness ratios in the 2 Si/Ge multilayer films were consistent with the RRT reference value within their expanded uncertainties.     

Evidence for the Existence of (SiP6H2)2– and its Homologs as Examples of Binary Nortricyclane‐Type Zintl Anions

The extraction of stoichiometric ternary K/Si/P, K/Ge/P, and K/Si/As solid mixtures with en/crypt‐222 afforded compounds with binary anions of the respective groups 14/15 elemental combination. Although the analysis of the products turned out to be extremely difficult owing to their intrinsically poor crystallinity and low solubility, we have evidence that one of them contains (SiP₆H₂)^2– anions. Preliminary data from the two other compounds indicate the existence of the heavier Ge/P and Si/As variants as well. The combination of all analytical results, including X‐ray crystallography, energy‐dispersive X‐ray (EDX) spectroscopy, electrospray ionization mass spectrometry (ESI‐MS), and nuclear magnetic resonance (NMR) spectroscopy, point towards the named composition of the anions and their doubly protonated nature. By this, they represent the first binary Zintl anions of the Si/P and Si/As elemental combination and complement the recent endeavors to synthesize binary Zintl anions of the light(er) p‐block elements. We discuss our attempts to elucidate the clusters' identity and provide our results as the most probable interpretation of the data, additionally corroborated by quantum chemical analyses.     

Reaction rate studies of atomic germanium (3P0,1) and silicon (3PJ) with various oxidizers

The gas phase reactions of Ge(³P_0,1) and Si(³P_J) with O₂, NO and N₂O have been studied in a flow tube system at 350 K. Atomic Ge and Si were produced by flowing GeH₄ and SiH₄ through a hollow cathode discharge. The subsequent disappearance of the Ge and Si atoms was followed with atomic absorption spectroscopy. Rate constants were determined for the reactions at 4 and 5 torr pressures.     

Ultrathin films of Ge on the Si(100)2 × 1 surface

The Ge/Si(100)2 × 1 interface was investigated by means of Auger electron spectroscopy, low‐energy electron diffraction, thermal desorption spectroscopy, and work function measurements, in the regime of a few monolayers. The results show that growth of Ge at room temperature forms a thermally stable amorphous interface without significant intermixing and interdiffusion into the substrate, for annealing up to ~1100 K. Therefore, the Ge‐Si interaction most likely takes place at the outmost silicon atomic plane. The charge transfer between Ge and Si seems to be negligible, indicating a rather covalent bonding. Regarding the Ge overlayer morphology, the growth mode depends on the substrate temperature during deposition, in accordance with the literature. Stronger annealing of the germanium covered substrate (>1100 K) causes desorption of not only Ge adatoms, but also SiGe and Ge₂ species. This is probably due to a thermal Ge‐Si interdiffusion. In that case, deeper silicon planes participate in the Ge‐Si interaction. Above 1200 K, a new Ge superstructure (4 × 4)R45^o was observed. Based on that symmetry, an atomic model is proposed, where Ge adatom pairs interact with free silicon dangling bonds.     

Concerning the silicon-germanium bond: mass spectral fragmentations of isomeric SiGe compounds R3EE′R3 (E  Si,E′  Ge,R  Ph,Me,(η5-C5H4)Fe (C5H5), (η5-C5H5)Fe(CO)2 and (η5-C9H7) Fe(CO)2)

Isomeric pairs of silicon-germanium compounds containing a SiGe bond (Me₃SiGePh₃ (I) and Ph₃SiGeMe₃ (II); FpSiMe₂GeMe₃ (III) and FpGeMe₂SiMe₃ (IV) (Fp = (η⁵-C₅H₅)Fe(CO)₂); IFpSiMe₂GeMe₃ (V) and IFpGeMe₂SiMe₃ (VI) (IFp = (η⁵-C₉H₇)Fe(CO)₂); IFpSiMe₂GePh₃ (VII) and IFpGeMe₂SiPh₃ (VIII) and the complex FcSiMe₂GeMe₂Fc (IX) (Fc = ferrocenyl) have been synthesized and examined by mass spectrometry.The R₃SiGeR′₃ compounds I and II exhibit considerable exchange of R groups to produce [R_3-nR′_nSi]⁺ and [R′_3-nR_nGe]⁺ ion in progressively lesser amounts as n = 1 → 2 → 3. For the metal-substituted complexes containing the grouping FeSiGe fragmentation occurs predominantly via SiGe bond cleavage with formation of ions containing the silylene ligand [FeSiR₂]⁺. Complexes with the FeGeSi backbone undergo preferential scission of the FeGe bond, illustrating the general bond strength trend FeSi > SiGe. Upon direct cleavage of the SiGe bond in R₃SiGeR₃ compounds, the percentage of the charge carried by [R₃Si]⁺ ions significantly exceeds that carried by [R₃Ge]⁺ ions, reflecting the greater electronegativity of Ge polarizing the SiGe bond.     

Etude systématique des relations entre les structures wadéite et tétragermanate

Systematic study of solid solutions with general formula A_2?xA_x′(B_1?zB_z′)Ge_3?ySi_yO₉ (A, A′ = K, Rb, Cs, Tl; B, B′ = Ge, Ti, Sn) has been carried out. These results allow us to propose a tridimensional diagram of existence of wadeite and tetragermanate structures, as a function of the sizes of A, B, Ge, and Si elements. Condition of stability based upon differences of sizes between A and M elements and B and M elements (M = Ge, Si) were found. The variation of compactness of wadeite and tetragermanate structures shows up the particular role of M element (Ge, Si).     

Some electroanalytical aspects of using pulse polarography for determination of Ge(IV)

Summary Presented data give some informations of analytical importance as a result of pulse polarographic investigations of Ge(IV) in KCl solutions within pH range 3–12 at Ge concentration from 1×10^–4 to 2.5×10^–6 M. It was shown that Ge(IV) can be polarographically active in acidic solution but its reduction interferes with hydrogen gas development. The addition ofp-quinone enables the determination of Ge(IV) without this interfering effect.Suggested explanation of the observed changes in polarographic curves dependent on pH and Ge concentration based on the existence of several polarographically active forms.

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Elektroanalytische Bemerkungen zur pulspolarographischen Bestimmung von Ge(IV)

Zusammenfassung Unsere Ergebnisse bieten einige Informationen über die pulspolarographische Bestimmung von Ge(IV) in KCl-Lösungen innerhalb pH 3–12 und bei Ge-Konzentrationen zwischen 10^–4 und 2,5×10^–6 M. Es wurde gezeigt, daß Ge(IV) in saurer Lösung polarographisch aktiv ist, seine Reduktion aber durch Wasserstoff-Entwicklung gestört wird. Der Zusatz vonp-Chinon beseitigt diese Störung. Die Änderung der polarographischen Kurven je nach Ge-Konzentration und pH beruht vermutlich auf der Existenz verschiedener polarographisch aktiver Formen.

     

New mixed heteropolytungstates containing Ge(IV) or Sn(IV)

New mixed heteropolyanions with formulae XZW₁₁O₃₉(OH)^m?[X = Si, Ge, B, As(V), Ga, Co(II), Zn; Z = Ge(IV), Sn(IV)] and X₂′ZW₁₇O₆₁(OH)^7?[X′= As(V), P(V);Z = Ge(IV), Sn(IV)] were prepared. Crystal systems of the potassium salts were determined. The stability range of the anions is given in terms of the pH. The acids corresponding to the salts were obtained and their neutralization studied. Spectroscopic and polarographic reduction studies are reported.     

Formation of236Pu,237Pu and238Pu isotopes by3He-induced nuclear reactions on uranium

The reaction U(³He, xn)Pu was studied by irradiating enriched²³⁵U (50.3%) and enriched²³⁸U (99.7%) targets with³He ions at the Åbo Akademi cyclotron (Turku, Finland). The incident³He ion energy in the irradiations was 27.0, 24.5 and 21.9 MeV. Plutonium was separated from the thin uranium targets by ion exchange. From the ion exchange fractions obtained, plutonium was electrodeposited on steel plates for alpha and X-ray counting. The activity of²³⁷Pu in the steel plates was determined with a Ge(Li) detector and the activity of²³⁶Pu and²³⁸Pu with a Si surface barrier detector. The cross sections of the reactions and the yields of plutonium isotopes are given.     

New Possible Applications of Heavy Main-Group Elements in Organic Synthesis

Aside from elements of the 2nd row, and one element of the 3rd row of the periodic system—Si, P, S, and Se, respectively, whose organoelement groups such as Me₃Si and Ph₃P^⊕ have proven useful in numerous organic syntheses—other elements of the 3rd as well as 4th and 5th row (Ge, As, Sn, Sb, Te, Pb, Bi) can also be used as components of synthetically useful organoelement groups, the elements As, Sn, and Pb, in particular, offering certain advntages over the others. Some of these organoelement groups are suitable equivalents for Li- or halogen-substituents attached to carbon; they stabilize carbanionic centers (minimum of this effect at the 3rd-row elements), and owing to their suitability as leaving groups in β-eliminations, also open up interesting synthetic possibilities. The thermally unduced syn- and silica-gel induced anti-elimination of Ph₃Sn, Ph₂Sb, Ph₃Pb, together with β-OH, are novel. With the newly synthesized compounds Ph_nEl—Ch₂—Li (El = Sn, Pb, As, Sb, Bi) and other α- and β-lithiated R_nEl- and Ph₂As(O)-reagents such organoelement groups can be introduced into organic compounds and exploited in organic and organoelement synthesis.     

Optimizing Cs-exchange in titanosilicate with the mineral pharmacosiderite topology: framework substitution of Nb and Ge

Titanosilicates with complete or partial substitution of Ge or Nb in the framework and having the mineral pharmacosiderite topology were hydrothermally prepared and their ion-exchange properties towards Cs were studied for Ti/Ge/Si, Ti/Si, Nb/Ti/Si and pure Ge phases. The basis for the differences in the ion exchange properties measured as distribution coefficients (K_d) for these materials are detailed via structural characterization using the Rietveld refinement technique on the X-ray powder diffraction data. The differences in affinity towards Cs⁺ result either from the degree of hydration of the exchanger resulting in different coordination environments or the position of cesium ion in the eight-ring channel.